JP2001106644A - Hydrophenanthrene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compound capable of effectively improving the stability of the liquid crystal phase within the temperature range, especially low temperatures by adding thereof, a liquid crystal composition and a liquid crystal display element having a wide temperature range by using the compound. SOLUTION: This hydrophenanthrene derivative is represented by formula (I). The nematic liquid crystal composition and liquid crystal display element comprise the derivative. One example of the derivative is represented by formula (II) (R is C3H7).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound which is a hydrophenanthrene derivative useful as an electro-optical liquid crystal display material and a liquid crystal composition using the same.

[0002]

2. Description of the Related Art Since the liquid crystal display element appeared as a calculator display, the development of computers has been progressed in the same way, and a large display capacity that could not be achieved in TN (Twisted Nematic) mode has been achieved by STN (Supertwisted Nematic). It has been widely used as an interface between computers and humans, depending on the mode. In addition, an active matrix liquid crystal display device (AM-
LCDs have high image quality that can be replaced by CRTs, and are expected to be the most promising displays with the backing of flattening and energy saving.

[0003] In recent years, the demand for notebook computers intended for portable use has increased, and in particular, ST computers used for these purposes have been used.
N-LCD and AM-LCD are required to have characteristics that can withstand outdoor use. For this reason, it has excellent characteristics of high contrast at high temperature, no crystal precipitation at low temperature and no manifestation of smectic phase, and no deterioration of contrast or display failure even when left under exposure to UV light or sunlight. Although strongly sought, conventional liquid crystal compounds and liquid crystal compositions did not always satisfy these requirements. In particular, the problem of crystal precipitation at low temperatures is serious, and the only way to avoid precipitation is to reduce the amount of liquid crystal compound added, and materials having excellent properties are often not fully utilized. ,
This is the most difficult problem to solve with a straight-ring type liquid crystal compound that has been widely used in the past. In other words, in a straight-ring type liquid crystal compound, a low crystal (or smectic)
No liquid crystal compound simultaneously satisfied the transition temperature, high nematic-isotropic transition temperature, high dielectric anisotropy, optimal elastic constant, and birefringence.

[0004]

An object of the present invention is to provide a compound capable of effectively improving the stability of a liquid crystal phase in a temperature range, particularly at a low temperature, by adding the compound. Another object of the present invention is to provide a liquid crystal composition and a liquid crystal display device having a wide temperature range using the compound.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present invention provides a novel liquid crystalline compound which is a hydrophenanthrene derivative represented by the general formula (I).

Invention 1 General formula (I)

Embedded image (In the formula, R is an alkyl or alkoxy group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, and 3 carbon atoms.
Represents an alkenyloxy group of ~ 16, or an alkyl group of 1 to 12 carbon atoms substituted with an alkoxy group of 1 to 10 carbon atoms, which may be substituted with halogen,
Ring A and ring C are each independently one C
H ₂ group or nonadjacent two or more CH ₂ groups -O- and or -S- in replaced by xylene group to be trans-1,4-cyclohexylene, present in group 1 CH Groups or two or more non-adjacent CH groups may be replaced by -N =
Phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, trans-decahydronaphthalene-trans -2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, which may be substituted with a cyano group or halogen,

Ring B is

Embedded image(Wherein the cyclohexane ring represents trans,
And it may be substituted with a halogen group or halogen. )
Represents the difference, L¹, L^TwoAnd L^ThreeAre independently -CH_Two-C
H_Two-, -C≡C-,-(CH_Two)_Four-, -CF = CF-, -OCH_Two-, -CH_TwoO-, -O
CF_Two-, -CF_TwoO-, -CO _Two-, -OCO-, -CH = N-N = CH-, -CH = CH-CH
_Two-CH_Two-, -CH_Two-CH_Two-CH = CH- or a single bond, m and
n independently represents 0 or 1, but m + n ≦ 1
X¹And X^TwoAre independently hydrogen and chlorine atoms
Y represents a hydrogen atom, a fluorine atom,
Chlorine atom, trifluoromethoxy group, difluoromethoxy
Si group, trifluoromethyl group, 2,2,2-trifluoroeth
Xy group, cyano group, linear alkyl having 1 to 12 carbon atoms
Group, a straight-chain alkenyl group having 2 to 12 carbon atoms and a straight-chain alkenyl group having 1 to 12 carbon atoms.
Chain alkyloxy group or 2 to 12 linear alkene
Represents a loxy group, and the constituent elements of this compound are
Where there is an asymmetric carbon
May be optically active or racemic,
Ring B represents tetradecahydrophenanthrene, Y is not substituted
Substituted alkyl, unsubstituted alkoxy or cyano
Represents a group, L^ThreeBut -CO_TwoX for-or -OCO-¹And X^Two
Either represents a chlorine atom or a fluorine atom, and ring A
Or a cyano group other than the 2- and 7-positions of ring C or ring B
L¹, L^TwoAnd L^ThreeAre independently -CH_Two-CH_Two-,-
(CH_Two)_Four-, -CF = CF-, -OCH_Two-, -CH_TwoO-, -OCF_Two-, -CF_TwoO-,
-CO_Two-, -OCO-, -CH = N-N = CH-, -CH = CH-CH_Two-CH_Two-, -CH_Two-C
H_Two-CH = CH- or a single bond. )
Enanthrene derivatives.

Invention 2 The invention according to invention 1, wherein ring A and ring C each independently represent a 1,4-phenylene group or a trans-1,4-cyclohexylene group which may be substituted by a fluorine atom. Compound. Invention 3 The compound according to Invention ¹ , wherein L ¹ , L ² and L ³ each independently represent —CH ₂ —CH ₂ — or a single bond. Invention 4 The compound according to Invention 1, wherein m and n represent 0.

Invention 5 In the general formula (I), ring B is

Embedded image (In the formula, the stereo structure of the cyclohexane ring represents trans, and the hydrogen atom on the aromatic ring may be substituted with a cyano group or a halogen.)
A compound as described.

Invention 6 In the general formula (I), ring B is

Embedded image (Wherein the stereochemistry of the cyclohexane ring represents trans, and the hydrogen atom on the aromatic ring may be substituted by a fluorine atom), wherein m and n represent 0. A compound as described.

Invention 7 The compound according to invention 6, wherein in formula (I), L ³ represents a single bond. Invention 8 In the general formula (I), R represents a linear alkyl group having 1 to 12 carbon atoms or a linear alkenyl group having 2 to 12 carbon atoms, Y is a fluorine atom, a chlorine atom, trifluoromethoxy A compound according to any one of Inventions 1 to 7, which represents a group, a trifluoromethyl group, a difluoromethoxy group, a 3,3,3-trifluoroethoxy group, or a cyano group.

Invention 9 In the general formula (I), R represents a linear alkyl group having 1 to 7 carbon atoms or a linear alkenyl group having 2 to 7 carbon atoms, and X ¹ and X ² are each independently Invention characterized by representing a hydrogen atom or a fluorine atom
9. The compound according to 1 to 8. Invention 10 The compound according to any one of Inventions 1 to 9, wherein in formula (I), Y represents a fluorine atom or a cyano group.

Invention 11 A liquid crystal composition containing at least one hydrophenanthrene derivative represented by the general formula (I) according to Inventions 1 to 10. Invention 12 A liquid crystal display device using the liquid crystal composition according to Invention 11. Invention 13 An active matrix driven liquid crystal display device using the liquid crystal composition according to Invention 11. Invention 14 An ultra-twisted nematic liquid crystal display device using the liquid crystal composition according to Invention 11.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The compound of the general formula (I) provided in the present invention preferably has the following forms.

In the general formula (I), R is an alkyl or alkoxy group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, and 3 to 16 carbon atoms which may be substituted with halogen. Represents an alkenyloxy group, or an alkyl group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, but represents a linear alkyl group having 1 to 12 carbon atoms or 2 to 2 carbon atoms. A straight-chain alkenyl group of 12 is preferable, a straight-chain alkyl group having 1 to 7 carbon atoms or a straight-chain alkenyl group having 2 to 7 carbon atoms is more preferable,
In the case of a linear alkenyl group, the following structure is particularly preferred.

Embedded image (The structural formula is connected to the ring at the right end.)

[0016] Ring A and ring C each independently, 2 or more CH ₂ groups not one CH ₂ group or adjacent present in group replaced by -O- and or -S- Good transformer-
1,4-cyclohexylene group, 1,4-phenylene group in which one CH group present in the group or two or more non-adjacent CH groups may be replaced by -N =, 1,4 -Cyclohexenylene,
1,4-bicyclo (2.2.2) octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,
6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6
-Diyl, which may be substituted with a cyano group or a halogen, preferably a 1,4-phenylene group or a trans-1,4-cyclohexylene group which may be substituted with a halogen, and a ring A In the above, a trans-1,4-cyclohexylene group is more preferable, and in ring C, a 1,4-phenylene group and a trans-1,4-cyclohexylene group are more preferable.

Ring B is

Embedded image (Wherein the steric of the cyclohexane ring represents trans, and the hydrogen atom on the aromatic ring may be substituted with a cyano group or a halogen).

Embedded image (A hydrogen atom on the aromatic ring may be substituted with a cyano group or halogen.)

Embedded image Is particularly preferred.

L ¹ , L ² and L ³ are each independently —CH ₂ —CH ₂
-, -C≡C-, -OCH _2- , -CH ₂ O-, -OCF _2- , -CF ₂ O- or a single bond, but in L ¹ and L ² -CH ₂ -CH _2- Or a single bond is preferable, and in L ³ , -CH ₂ -CH _2- , -C≡C-
Alternatively, a single bond is preferable, and a single bond is particularly preferable. m
And n each independently represent 0 or 1, and m + n ≦ 1, but it is preferred that m and n represent 0. X ¹ and X ² each independently represent a hydrogen atom, a chlorine atom or a fluorine atom, preferably a hydrogen atom or a fluorine atom,
More preferably, one of X ¹ and X ² represents a fluorine atom.

Y is a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethyl group, a 3,3,3-trifluoroethoxy group, a cyano group, or a straight-chain having 1 to 12 carbon atoms. A linear alkyl group, a linear alkenyl group having 2 to 12 carbon atoms, a linear alkyloxy group having 1 to 12 carbon atoms or a linear alkenyloxy group having 2 to 12 carbon atoms, such as a fluorine atom, a chlorine atom, Fluoromethoxy group, difluoromethoxy group, trifluoromethyl group, 3,
A 3,3-trifluoroethoxy group and a cyano group are preferred, a fluorine atom, a trifluoromethoxy group and a cyano group are more preferred, and a fluorine atom or a cyano group is particularly preferred.

As described above, the compound of the general formula (I)
The choice of R, ring A, ring B, ring C, L ¹ , L ² , L ³ , m, n, X ¹ , X ² and Y can encompass a very wide variety of compounds, but these Among them, compounds represented by the following general formulas (Iaa) to (Ihx) are preferable.

[0021]

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[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

The compound of the general formula (I) can be produced as follows. 1. Production of general formula (I) having tetradecahydrophenanthrene skeleton

1-1. Production of General Formula (Iaf) from General Formula (Iaa) General Formula (II)

Embedded image (Wherein R represents the same meaning as in (I), and the steric of the cyclohexane ring represents trans.)

Embedded image (In the formula, X ¹ , X ² and Y have the same meaning as in (I), except for a cyano group, where M is MgX (X represents a chlorine atom, a bromine atom, an iodine atom) or Li Etc. metal atom, B
(OH) ₂ represents SiF (CH ₃ ) ₂ . After reacting the compound of
General formula that can be produced by dehydration in the presence of an acid catalyst
(IVa) and general formula (IVb)

Embedded image (In the formula, R, X ¹ , X ² and Y represent the same meaning as in (I), and the steric of the cyclohexane ring represents trans.) After catalytic reduction using a transition metal catalyst such as palladium carbon, potassium By isomerization using a strong base such as -t-butoxide, the above-mentioned general formula (Iaa)
Formula (Ia-1) containing a compound of

Embedded image Wherein R, X ¹ , X ² and Y have the same meanings as in (I), and the stereo of the cyclohexane ring represents trans.

1-2. Preparation of general formula (Iao) from general formula (Iaj)

Embedded image After reacting the compound represented by the general formula (VIa) obtained by hydrolysis in the presence of an acid catalyst and isomerization with a base

Embedded image (In the formula, R represents the same meaning as in (I), and the steric shape of the cyclohexane ring represents trans.) After reacting the formula (V) again, the compound is obtained by hydrolysis in the presence of an acid catalyst. Expression (V
Ib)

Embedded image (Wherein, R has the same meaning as in (I), and the steric shape of the cyclohexane ring represents trans.) After reacting with the general formula (III), a compound obtained by dehydration in the presence of an acid catalyst, Formula (VII)

Embedded image (Wherein, R, X ¹ , X ² and Y represent the same meaning as in (I), and the steric shape of the cyclohexane ring represents trans.) By catalytic reduction using a transition metal catalyst such as palladium carbon. General formula (Ia-2) containing a compound of the general formula (Iao) from the general formula (Ia-2)

Embedded image Wherein R, X ¹ , X ² and Y have the same meanings as in (I), and the stereo of the cyclohexane ring represents trans.

1-3. Production of general formula (Iai) from general formula (Iag) and general formula (Iar) from general formula (Iap)

The general formula (VIII) is replaced by the general formula (VIII)

Embedded image Wherein X ¹ has the same meaning as in (I) and M has the same meaning as in (III).

Embedded image (Wherein R and X ¹ have the same meanings as in (I), and the steric shape of the cyclohexane ring represents trans.) A general formula (X) obtained by dehydrating with phosphorus oxychloride or the like.

Embedded image (Wherein R and X ¹ have the same meanings as in (I), and the steric shape of the cyclohexane ring represents trans.) By reducing in the presence of a catalyst such as Raney nickel, palladium carbon, etc., from the general formula (Iag) General formula (I) including general formula (Iai)
a-3)

Embedded image Wherein R and X ¹ have the same meanings as in (I), and the cyclohexane ring stereo represents trans. Using general formula (VI) instead of general formula (II), similarly to general formula (Ia-4) including general formula (Iar) from general formula (Iap)

Embedded image Wherein R and X ¹ have the same meanings as in (I), and the cyclohexane ring stereo represents trans.

1-4. Preparation of general formula (Iai) and general formula (Iar)

Compounds of the formula (Ia-1) in which Y has been represented by the formula (Ia-1a)

Embedded image (In the formula, R, X ¹ and X ² have the same meaning as in (I), except for the case of a hydrogen atom, except that the steric shape of the cyclohexane ring represents trans.) And then reacting with carbon dioxide to obtain the general formula (XI)

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I), except for the case of a hydrogen atom, and the steric shape of the cyclohexane ring represents trans.) General formula (XII) obtained by reacting

Embedded image (In the formula, R, X ¹ and X ² have the same meaning as in (I), except for the case of a hydrogen atom, and the stereo of the cyclohexane ring represents trans.) Formula (Ia-5) including General Formula (Iai)

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I),
The configuration of the cyclohexane ring represents trans. ) Can be manufactured.

The general formula (Ia-1b) is replaced with the general formula (Ia-1b)

Embedded image (Wherein, R, X ¹ and X ² have the same meanings as in (I), except for the case of a hydrogen atom, and the stereostructure of the cyclohexane ring represents trans.) General formula (Ia-6) containing

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I),
The configuration of the cyclohexane ring represents trans. ) Can be manufactured.

1-5. Production of General Formula (Iau) from General Formula (Ias) The general formula (XIII) obtained by reacting an oxidizing agent such as silver oxide with the general formula (VIa) whose production method has already been described. )

Embedded image (Wherein, R represents the same meaning as in (I), and the steric shape of the cyclohexane ring represents trans.) After acid chloride, the compound represented by the general formula (XIV)

Embedded image (Wherein X ¹ , X ² and Y have the same meaning as in (I))
By reacting the compound of the general formula (Ias)
General formula (Ia-7) including (Iau)

Embedded image Wherein R, Y, X ¹ and X ² have the same meanings as in (I), and the stereo of the cyclohexane ring represents trans.

1-6. Preparation of General Formula (Iai) from General Formula (Iaa) General Formula (XV)

Embedded image A compound represented by the general formula which can be produced by reacting a secondary amine such as pyrrolidine with a secondary amine such as pyrrolidine, reacting with methyl vinyl ketone, cyclizing under acidic conditions, and reducing with metallic lithium or the like. (XVI)

Embedded image (In the formula, the stereo configuration of the cyclohexane ring represents trans.)
Then, after reacting with the general formula (III), dehydration in the presence of an acidic catalyst, followed by reduction in the presence of a metal catalyst such as palladium carbon, and then isomerization under basic conditions, thereby obtaining the general formula (XVII )

Embedded image (Wherein, Y, X ¹ and X ² represent the same meaning as in (I),
The configuration of the cyclohexane ring represents trans. ).
This is hydrolyzed under acidic conditions to remove the protecting group of the carbonyl group, and represented by the general formula (XVIII)

Embedded image (Wherein, Y, X ¹ and X ² represent the same meaning as in (I),
The configuration of the cyclohexane ring represents trans. ) Is obtained. This is reacted with the formula (V), hydrolyzed under acidic conditions, and subsequently isomerized under basic conditions to obtain a compound of the general formula (XIX)

Embedded image (Wherein, Y, X ¹ and X ² represent the same meaning as in (I),
The configuration of the cyclohexane ring represents trans. ) Is obtained. After repeating the step of reacting and hydrolyzing the formula (V) an arbitrary number of times, the general formula (XX)

Embedded image (Wherein R ′ represents an alkyl group or an alkoxy group having 1 to 15 carbon atoms.) The general formula (Iaa) to the general formula (Iai) having any alkenyl group by reacting Ia-
8)

Embedded image (Wherein, R ′ has the same meaning as in (XX), Y, X ¹ and
X ² has the same meaning as in (I), and the stereo of the cyclohexane ring represents trans. ) Can be manufactured.

2. Preparation of general formula (I) having 1,2,3,4,4a, 9,10,10a-octahydrophenanthrene skeleton

2-1. Production of General Formula (Ibc) from General Formula (Iba) and General Formula (Icc) from General Formula (Ica) 1 General Formula (XXX)

Embedded image (Wherein, R represents the same meaning as in (I), and the steric shape of the cyclohexane ring represents trans.) The compound represented by the general formula is subjected to demethoxylation using hydrobromic acid or the like.
(XXXI)

Embedded image (Wherein, R has the same meaning as in (I), and the steric of the cyclohexane ring represents trans.). This is reacted with trifluoromethanesulfonic anhydride or the like to give a compound of the general formula (XXXII)

Embedded image (In the formula, R represents the same meaning as in (I), Z represents a leaving group such as a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group or a p-toluenesulfonyloxy group, and a cyclohexane ring Is represented by trans.), And then reacted with the general formula (III) in the presence of a transition metal catalyst such as tetrakistriphenylphosphine palladium (0) to obtain a compound represented by the general formula
(Iba) to general formula (Ibc) and general formula (Ica) to general formula (Icc)
General formula (Ib-1) containing

Embedded image Wherein R, Y, X ¹ and X ² have the same meanings as in (I), and the stereo of the cyclohexane ring represents trans.

2-2. Preparation of General Formula (Ibc) from General Formula (Iba) and General Formula (Icc) from General Formula (Ica) 2 General Formula (XXXIII)

Embedded image (Wherein, R represents the same meaning as in (I), and the steric shape of the cyclohexane ring represents trans.), Reacted with the general formula (III), and then dehydrated to obtain the general formula (XXX
IV)

Embedded image (In the formula, R, Y, X ¹ and X ² represent the same meaning as in (I), but except for the case where Y is a cyano group, the stereo structure of the cyclohexane ring represents trans.), Bromine, DDQ ( 2,3-dichloro-5,
By oxidation using an oxidizing agent such as 6-dicyano-1,4-benzoquinone), chloranil (tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzoquinone), the general formula
(Iba) to general formula (Ibc) and general formula (Ica) to general formula (Icc)
General formula (Ib-1) containing

2-3. Preparation of General Formula (Ibo) from General Formula (Ibm) and General Formula (Ico) from General Formula (Icm) General Formula (XXXV)

Embedded image (In the formula, Y, X ¹ and X ² represent the same meaning as in (I).)
Is reacted with a general formula (XXXII) in the presence of a transition metal catalyst such as tetrakistriphenylphosphine palladium (0), thereby converting the general formula (Ibm) to the general formula (Ibo) and the general formula (Ibo).
General formula (Ib-2) including general formula (Ico) from (Icm)

Embedded image Wherein R, Y, X ¹ and X ² have the same meanings as in (I), and the stereo of the cyclohexane ring represents trans.

2-4. Preparation of General Formula (Ibi) from General Formula (Ibd) and General Formula (Ici) from General Formula (Icd) The general formula (XVI) was halogenated using an electrophilic halogenating agent. Compound, general formula (XXXVI)

Embedded image (In the formula, R represents the same meaning as in (I), X ³ and X ⁴ each independently represent a hydrogen atom, a fluorine atom and a chlorine atom, but at least one of X ³ or X ⁴ is a hydrogen atom And the steric form of the cyclohexane ring represents trans.). The electrophilic halogenating agent used here is typically bromine, chlorine gas, fluorine gas or xenon fluoride, or an NEC such as MEC reagent (manufactured by Daikin Industries, Ltd.) or ACCUFLOR NFPy (manufactured by AlliedSignal). -Fluoropyridinium derivative or ACCUFLOR NFTh, ACCUFLOR NF
Si (made by AlliedSignal), F-TEDA-BF4 (made by AIR PRODUCTS) and the like.

The general formula (XXXVI) is reacted with trifluoromethanesulfonic anhydride or the like to give the general formula (XXXVI).
VII)

Embedded image (Wherein, R represents the same meaning as in (I), and X ³ and X ⁴ represent
(XXXVI) represents the same meaning as in, Z is a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group,
It represents a leaving group such as a benzenesulfonyloxy group or a p-toluenesulfonyloxy group, and the stereo structure of the cyclohexane ring represents trans. ), The general formula (III) is reacted in the presence of a transition metal catalyst such as tetrakistriphenylphosphine palladium (0), and the obtained isomer is separated by column chromatography, thereby obtaining the general formula (Ibm) From the general formula
(Ibo) and the general formula (Ib) including the general formula (Ico) from the general formula (Icm)
-3)

Embedded image (In the formula, R, Y, X ¹ and X ² have the same meaning as in (I), X ³ and X ⁴ have the same meaning as in (XXXVI), and the stereo structure of the cyclohexane ring represents trans.) Can be manufactured.

2-5. Production of general formula (Ibu) from general formula (Ibp) and general formula (Icu) from general formula (Icp) General formula (XXXVII) is converted to general formula (XXXV) by tetrakistriphenylphosphine palladium (0) and the like, and the obtained isomers are separated by column chromatography, whereby the general formula (Ibp) is converted from the general formula (Ibu) and the general formula (Icp) from the general formula (Icp). General formula (Ib-4) containing

Embedded image (In the formula, R, Y, X ¹ and X ² have the same meaning as in (I), X ³ and X ⁴ have the same meaning as in (XXXVI), and the stereo structure of the cyclohexane ring represents trans.) Can be manufactured.

2-6. Preparation of General Formula (Ibl) from General Formula (Ibj) and General Formula (Icl) from General Formula (Icj) General Formula (XXXVIII)

Embedded image (Wherein X ⁵ and X ⁶ each independently represent a fluorine atom or a chlorine atom.) A compound represented by the general formula (XXXIX) is reacted with a secondary amine such as pyrrolidine to give an enamine.

Embedded image Wherein X ⁵ and X ⁶ have the same meaning as in (XXXVIII). This can be produced by reacting with methyl vinyl ketone and then cyclizing under acidic conditions.

Embedded image (Wherein X ⁵ and X ⁶ represent the same meaning as in (XXXVIII).)

Embedded image Wherein X ⁵ and X ⁶ have the same meanings as in (XXXVIII), which is reacted with formula (V), then hydrolyzed under acidic conditions and subsequently under basic conditions. By isomerization, the compound represented by the general formula (XLII)

Embedded image (Wherein X ⁵ and X ⁶ represent the same meaning as in (XXXVIII), and the steric ring of the cyclohexane ring represents trans.). The compound of the general formula (XX) is reacted with the compound of the general formula (XLIII).

Embedded image (In the formula, R ′ has the same meaning as in (XX), and X ⁵ and X ⁶
Has the same meaning as in (XXXVIII), and the steric of the cyclohexane ring represents trans. ).

Here, it is also possible to produce an arbitrary alkenyl group by reacting the formula (XX) with the formula (V) instead of the formula (XX) and then reacting the formula (XX). It is. The general formula (XLIII) is catalytically reduced using a transition metal catalyst such as palladium carbon to obtain the general formula (XLIV)

Embedded image (Wherein, R represents the same meaning as in (I), and X ⁵ and X ⁶ represent
It has the same meaning as in (XXXVIII), and the stereo of the cyclohexane ring represents trans. ). This compound is
General formula obtained by reacting with bromine or iodine after lithiation with alkyl lithium such as butyl lithium
(XLV)

Embedded image (Wherein, R represents the same meaning as in (I), and X ⁵ and X ⁶ represent
XXXX has the same meaning as in (XXXVIII), X ⁷ represents a bromine atom or an iodine atom, and the steric of the cyclohexane ring represents trans. ) And the general formula (Ib-5) including the general formula (Ib) from the general formula (Ibl) and the general formula (Icj) by reacting the general formula (III)

Embedded image (Wherein, R, X ¹ , X ² and Y represent the same meaning as in (I), X ⁵ and X ⁶ represent the same meaning as in (XXXVIII),
The configuration of the cyclohexane ring represents trans. ) Can be manufactured.

2-7. Preparation of general formula (Ida) and general formula (Idb) General formula (XLVI) obtained by reacting general formula (XXXII) with general formula (VIII)

Embedded image (Wherein R and X ¹ have the same meanings as in (I), and the steric shape of the cyclohexane ring represents trans.) By removing the protecting group using phosphorus oxychloride or the like to obtain the general formula (Ida)
And the general formula (1d-1) including the general formula (Idb)

Embedded image Wherein R and X ¹ have the same meanings as in (I), and the cyclohexane ring stereo represents trans.

By reacting the general formula (XXXIII) with the general formula (VIII),

Embedded image (Wherein R and X ¹ have the same meanings as in (I), and the steric shape of the cyclohexane ring represents trans.), Which is reacted with phosphorus oxychloride or the like to perform deprotection and dehydration. General formula (XLVIII)

Embedded image (Wherein R and X ¹ have the same meanings as in (I), and the steric of the cyclohexane ring represents trans). Oxidizing agents such as bromine, DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone), chloranil (tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzoquinone) By oxidizing with the general formula (Ida) and the general formula (Idb)
General formula (Id-1) containing

2-8. Production of General Formula (Idc) Compound of the general formula (Id-1) in which Y is a hydrogen atom in the general formula (Id-1) whose production method has already been described.

Embedded image (In the formula, R, X ¹ and X ² have the same meaning as in (I), except for the case of a hydrogen atom, except that the steric shape of the cyclohexane ring represents trans.) After reacting with carbon dioxide, the general formula (XLIX)

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I), except for the case of a hydrogen atom, and the steric shape of the cyclohexane ring represents trans.) General formula (L) obtained by reacting

Embedded image (In the formula, R, X ¹ and X ² have the same meaning as in (I), except for the case of a hydrogen atom, and the stereo of the cyclohexane ring represents trans.) General formula (Id-2) including general formula (Idc)

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I),
The configuration of the cyclohexane ring represents trans. ) Can be manufactured.

2-9. Production of general formula (Ibi) from general formula (Ibd) and general formula (Ici) from general formula (Icd) Transition metal such as tetrakistriphenylphosphine palladium (0) is added to general formula (XXXVI) By reacting the general formula (VIII) in the presence of a catalyst, the general formula (LI)

Embedded image Wherein R and X ¹ have the same meanings as in (I), X ³ and X ⁴ have the same meanings as in (XXXVI), and the cyclohexane ring stereo represents trans. General formula (LI)
Is deprotected using phosphorus oxychloride or the like, and the resulting mixture of isomers is separated by column chromatography, whereby the general formula (Idd) is converted to the general formula (Ide) and the general formula (Idg) is converted to the general formula
General formula (Id-3) including (Idh)

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I), and X
³ and X ⁴ represent the same meaning as in (XXXVI), solid cyclohexane rings represent trans. ) Can be manufactured.

2-10. Preparation of General Formula (Idf) and General Formula (Idi) Compounds in which Y is a hydrogen atom in general formula (Ib-3) which has already been described in the general formula (Ib-3a)

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I), except for a hydrogen atom, X ³ and X ⁴ represent the same meaning as in (XXXVI), and Represents trans.) Is lithiated with an alkyl lithium such as butyl lithium, and then reacted with carbon dioxide to obtain a compound of the general formula (XI)

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I), except for a hydrogen atom, X ³ and X ⁴ represent the same meaning as in (XXXVI), and Represents trans.) Is converted to an acid chloride, and then reacted with ammonia to obtain a compound represented by the general formula (XII):

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I), except for a hydrogen atom, X ³ and X ⁴ represent the same meaning as in (XXXVI), and Represents trans.) By dehydration using phosphorus oxychloride or the like to obtain a compound represented by the general formula (Id) including the general formula (Idf) and the general formula (Idi).
d-4)

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I), except for a hydrogen atom, X ³ and X ⁴ represent the same meaning as in (XXXVI), and Represents trans.) Can be produced.

2-11. Production of Formulas (Idj) and (Idk) Reaction of Formula (XLV) with Formula (VIII) in the presence of a transition metal catalyst such as tetrakistriphenylphosphine palladium (0) By the general formula (LI)

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I), and X
⁵ and X ⁶ represent the same meaning as in (XXXIX), solid cyclohexane rings represent trans. ). General formula (LI
By deprotecting V) with phosphorus oxychloride or the like, the general formula (Id-5) including the general formula (Idj) and the general formula (Idk)

Embedded image (Wherein, R, X ¹ and X ² represent the same meaning as in (I), and X
⁵ and X ⁶ represent the same meaning as in (XXXIX), solid cyclohexane rings represent trans. ) Can be manufactured.

2-12. Production of General Formula (Idl) Compound of the general formula (Ib-3b) in which Y is a hydrogen atom in the general formula (Ib-3) whose production method has already been described.

Embedded image (Wherein, R represents the same meaning as in (I), and X ⁵ and X ⁶ represent
X ⁸ and X ⁹ each independently represent a fluorine atom or a chlorine atom, and the stereo structure of the cyclohexane ring represents trans. ) Is lithiated with an alkyl lithium such as butyl lithium and then reacted with carbon dioxide to obtain a general formula (LV)

Embedded image (Wherein, R represents the same meaning as in (I), and X ⁵ and X ⁶ represent
X ⁸ and X ⁹ each independently represent a fluorine atom or a chlorine atom, and the stereo structure of the cyclohexane ring represents trans. ) Is converted to an acid chloride and then reacted with ammonia to obtain a general formula (LV)
I)

Embedded image (Wherein, R represents the same meaning as in (I), and X ⁵ and X ⁶ represent
X ⁸ and X ⁹ each independently represent a fluorine atom or a chlorine atom, and the stereo structure of the cyclohexane ring represents trans. ), The general formula (Id-6) including the general formula (Idl) by dehydration using phosphorus oxychloride or the like

Embedded image (Wherein, R represents the same meaning as in (I), and X ⁵ and X ⁶ represent
X ⁸ and X ⁹ each independently represent a fluorine atom or a chlorine atom, and the stereo structure of the cyclohexane ring represents trans. ) Can be manufactured.

2-13. Production of General Formula (Ido) from General Formula (Idm) and General Formula (Idu) from General Formula (Idp) General Formula (LV)

Embedded image (Wherein X ³ and X ⁴ represent the same meaning as in (XXXVI).) The compound represented by the general formula (LVI) is reacted with a secondary amine such as pyrrolidine to give an enamine.

Embedded image Wherein X ³ and X ⁴ have the same meaning as in (XXXVI).

The compound represented by the general formula (LVII) can be produced by reacting with methyl vinyl ketone and cyclizing it under acidic conditions.

Embedded image (Wherein X ³ and X ⁴ have the same meanings as in (XXXVI).)

Embedded image Wherein X ³ and X ⁴ have the same meaning as in (XXXVI). By isomerization, the compound represented by the general formula (LIX)

Embedded image (Wherein X ³ and X ⁴ represent the same meaning as in (XXXVI),
The configuration of the cyclohexane ring represents trans. ) Is obtained. This compound is reacted with the general formula (XX),
General formula (LX)

Embedded image (Wherein R ′ has the same meaning as in (XX), and X ³ and X ⁴
Represents the same meaning as in (XXXVI), and the steric of the cyclohexane ring represents trans. ). Where the general formula
After repeating the step of reacting and hydrolyzing the formula (V) in place of the (XX), it is also possible to produce an arbitrary alkenyl group by reacting the general formula (XX).

The general formula (LX) is subjected to catalytic reduction using a transition metal catalyst such as palladium carbon to obtain the general formula (LXI)

Embedded image (Wherein, R represents the same meaning as in (I), and X ³ and X ⁴ represent
It has the same meaning as in (XXXVI), and the steric of the cyclohexane ring represents trans. ). General formula (LXII) obtained by reacting this compound with oxalic acid dichloride in the presence of a Lewis acid catalyst such as aluminum chloride

Embedded image (Wherein, R represents the same meaning as in (I), and X ³ and X ⁴ represent
Represents the same meaning as in (XXXVI). ) And the general formula (III), and if the isomers are present, include the general formula (Ido) from the general formula (Ido) and the general formula (Idp) from the general formula (Idm) by separation by column chromatography. General formula (Id-7)

Embedded image (In the formula, R, X ¹ , X ² and Y have the same meaning as in (I), X ³ and X ⁴ have the same meaning as in (XXXVI), and the stereo structure of the cyclohexane ring represents trans.) Can be manufactured.

2-14. Production of general formula (Idx) from general formula (Idv) After lithiation of general formula (XLIV) with an alkyl lithium such as butyllithium, the general formula (LXIII) obtained by reacting carbon dioxide gas )

Embedded image (Wherein, R represents the same meaning as in (I), and X ⁵ and X ⁶ represent
It has the same meaning as in (XXXIX), and the steric of the cyclohexane ring represents trans. ) Is reacted with the general formula (XIV) to obtain the general formula (Idv).
General formula (Id-8) including (Idx)

Embedded image (In the formula, R, Y, X ¹ and X ² have the same meaning as in (I), X ⁵ and X ⁶ have the same meaning as in (XXXIX), and the stereo structure of the cyclohexane ring represents trans.) Can be manufactured.

3. Preparation of general formula (I) having 1,2,3,4-tetrahydrophenanthrene skeleton Formula (LXIV)

Embedded image By reacting the compound represented by a halogenating agent such as thionyl chloride, the formula (LXV)

Embedded image Get. By reacting this with ethylene gas in the presence of a Lewis acid such as aluminum chloride, the formula (LXVI)

Embedded image After obtaining, the general formula (LXVII)

Embedded image (Wherein, R represents the same meaning as in (I), M represents MgX (X represents a chlorine atom, bromine atom, iodine atom) or Li
And the like, such as B (OH) ₂ and SiF (CH ₃ ) ₂ . After reacting the compound of the formula (LXVIII)

Embedded image (In the formula, R represents the same meaning as in (I).) After reducing the double bond using a transition metal catalyst such as palladium carbon, isomerization is performed using a strong base such as potassium-t-butoxide. By the general formula (LXIX)

Embedded image Wherein R represents the same meaning as in (I), and the stereo of the cyclohexane ring represents trans.

Further, after reacting the formula (LXV) with the formula (V), the compound is hydrolyzed under acidic conditions and then isomerized under basic conditions to obtain the formula (LXX)

Embedded image (Wherein the steric of the cyclohexane ring represents trans). This compound is reacted with the general formula (XX) to obtain a compound represented by the general formula (LXXI)

Embedded image (Wherein R ′ has the same meaning as in formula (XX) and the steric ring of the cyclohexane ring represents trans).

Here, it is possible to produce an arbitrary alkenyl group by reacting the formula (XX) with the formula (V) instead of the formula (XX) and then reacting with the formula (XX). It is. Obtained general formula (LXIX) or general formula (LXXI)
Is subjected to deprotection of phenol using hydrobromic acid or the like to give a compound of the general formula (LXXII)

Embedded image Wherein R represents the same meaning as in (I), and the stereo of the cyclohexane ring represents trans. This is reacted with the same halogenating agent as used in the production of the general formula (XXXVI) to give the general formula (LXXIII)

Embedded image (Wherein, R, X ³ and X ⁴ represent the same meaning as in (I),
The configuration of the cyclohexane ring represents trans. ) Can be manufactured. The obtained general formula (LXXII) is described above as 1,2,3,4,4a, 9,1
General formula having 0,10a-octahydrophenanthrene skeleton
The compound having the corresponding 1,2,3,4-tetrahydrophenanthrene skeleton can be produced by substituting the general formula (XXXI) described in the production of (I). In addition, the corresponding compound can be produced by using general formula (LXXIII) instead of general formula (XXXVI).

4. Preparation of general formula (I) having 1,2,3,4,5,6,7,8-octahydrophenanthrene skeleton Formula (LXXIV)

Embedded image By partially reducing the aromatic ring with hydrogen in the presence of a metal catalyst such as palladium, ruthenium, and platinum, the compound represented by the formula (LXXV)

Embedded image Get. Formula (LXXVI) in which only one of the carbonyl groups of this compound is protected with a diol

Embedded image After obtaining the general formula (LXXVII) by reacting the general formula (LXVII) and dehydration in the presence of an acid catalyst

Embedded image Wherein R represents the same meaning as in (I). By reducing the double bond of this compound with hydrogen in the presence of a metal catalyst, a compound represented by the general formula (LXXVIII)

Embedded image Wherein R represents the same meaning as in (I). By deprotecting this compound in the presence of an acid catalyst, the compound represented by the general formula (LXXIX)

Embedded image Wherein R represents the same meaning as in (I). By using the obtained general formula (LXXIX) instead of the general formula (II) described in the preparation of the general formula (I) having a tetradecahydrophenanthrene skeleton described above,
A compound having a 1,2,3,4,5,6,7,8-octahydrophenanthrene skeleton can be produced.

Many of the compounds represented by the general formula (I) exhibit excellent compatibility with other liquid crystal materials, and thus are suitably used as a material for a liquid crystal display cell in a state of a mixture with other liquid crystal compounds. be able to. The compound (I) can be used in any of the various display methods described above, but is suitable for use in a TN display element driven by a simple matrix or an active matrix and an STN display element.

As a preferred representative example of the nematic liquid crystal compound which can be used by mixing with the compound represented by the general formula (I), the composition provided by the present invention includes the first component At least one compound represented by the general formula (I), and as other components, it is particularly preferable to include at least one compound from the following second to fourth components.

That is, the second component is a so-called fluorine-based (halogen-based) p-type liquid crystal compound, which is represented by the following general formula (A1).
It consists of the compound represented by (A3).

Embedded image In the above formula, ^Rb represents an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch and have a 3- to 6-membered ring structure. Any -CH _2- present in the group may be -O-, -CH = CH-, -CH = CF-, -CF = C
H-, may be replaced by -CF = CF- or -C 交換 C-,
Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but may be a straight-chain alkyl group having 2 to 7 carbon atoms or a straight-chain alkyl group having 2 to 7 carbon atoms. An alkenyl group, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, the terminal of which is substituted by an alkoxy group having 1 to 3 carbon atoms. Also,
When an asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring A, ring B and ring C are each independently substituted by a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, and one or more fluorine atoms. 1,4-phenylene group, naphthalene-2,6- which may be substituted by one or more fluorine atoms
Diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane- Trans-2,5-diyl group, pyrimidine
Represents a -2,5-diyl group or a pyridine-2,5-diyl group,
Trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group or 1 which may be substituted by a fluorine atom
A 1,4-phenylene group which may be substituted by 1 to 2 fluorine atoms is preferred. In particular, when ring B is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group, ring A is trans-1,4-
It is preferably a cyclohexylene group, and when ring C is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group, ring B and ring A are trans-1 It is preferably a 4,4-cyclohexylene group. Further, in (A3), ring A is preferably a trans-1,4-cyclohexylene group.

L ^a , L ^b and L ^c are linking groups, each independently being a single bond, an ethylene group (—CH ₂ CH ₂ —), a 1,2-propylene group.
_{(-CH (CH 3) CH 2} - and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO
-, -OCO-, -OCF _2- , -CF ₂ O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF =
Represents CF-, -C≡C- or -CH = NN = CH-, but has a single bond, an ethylene group, a 1,4-butylene group, -COO-, -OCF _2- , -CF ₂ O-, -CF = CF- or -C≡C- is preferred, and a single bond or an ethylene group is particularly preferred. In (A2), at least one of them is (A3)
In, at least two of them preferably represent a single bond.

Ring Z is an aromatic ring and has the following general formulas (La) to (L)
It can be represented by c).

Embedded image In the formula, Y ^{a to} Y ^j each independently represent a hydrogen atom or a fluorine atom, and in (La), at least one of ^Ya and Y ^b
Is preferably a fluorine atom, and in (Lb), Y ^d
At least one to Y ^f is preferably a fluorine atom, and further preferably in particular Y ^d is a fluorine atom.

[0069] end group P ^a represents a fluorine atom, a chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group or 2 or more fluorine atoms optionally substituted carbon atoms 2 or 3 alkoxy Represents a group, an alkyl group, an alkenyl group or an alkenyloxy group, preferably a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group, particularly preferably a fluorine atom. In (A2), the compound of the general formula (I) of the present invention is excluded.

The third component is a so-called cyano-based p-type liquid crystal compound, which is a compound represented by the following general formulas (B1) to (B3).

Embedded image In the above formula, R ^c represents an alkyl group having 1 to 12 carbon atoms, which may have a methyl or ethyl branches may be linear, have a cyclic structure having 3 to 6-membered ring Any -CH _2- present in the group may be -O-, -CH = CH-, -CH = CF-, -CF = C
H-, may be replaced by -CF = CF- or -C 交換 C-,
Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but may be a straight-chain alkyl group having 2 to 7 carbon atoms or a straight-chain alkyl group having 2 to 7 carbon atoms. An alkenyl group, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, the terminal of which is substituted by an alkoxy group having 1 to 3 carbon atoms. Also,
When an asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring D, ring E and ring F are each independently substituted by a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, and one or more fluorine atoms. 1,4-phenylene group, naphthalene-2,6- which may be substituted by one or more fluorine atoms
Diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane- Trans-2,5-diyl group, pyrimidine
Represents a -2,5-diyl group or a pyridine-2,5-diyl group,
Trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group or 1 which may be substituted by a fluorine atom
A 1,4-phenylene group which may be substituted by 1 to 2 fluorine atoms is preferred. In particular, when Ring E is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, Ring D is trans-1,4-
It is preferably a cyclohexylene group, and when ring F is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group, ring D and ring E are trans-1 It is preferably a 4,4-cyclohexylene group. Further, in (B3), ring D is preferably a trans-1,4-cyclohexylene group.

L ^d , ^Le and L ^f are linking groups, each independently being a single bond, an ethylene group (—CH ₂ CH ₂ —), a 1,2-propylene group.
_{(-CH (CH 3) CH 2} - and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO
-, -OCO-, -OCF _2- , -CF ₂ O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF =
CF -, - C≡C -, - OCH 2 -, - CH 2 O-, or represent a -CH = NN = CH-,
A single bond, an ethylene group, —COO—, —OCF ₂ —, —CF ₂ O—, —CFCFCF— or —C≡C— is preferred, and a single bond, an ethylene group or —COO— is particularly preferred. Further, in (B2), at least one of them preferably represents a single bond in (B3).

Ring Y is an aromatic ring represented by the following general formulas (Ld) to (L
f).

Embedded image In the formula, Y ^{k to} Y ^q each independently represent a hydrogen atom or a fluorine atom, but in (Le), Y ⁿ and ^Yo are preferably hydrogen atoms. The terminal group Pa represents ^a cyano group (—CN), a cyanato group (—OCN) or —C≡CCN, and a cyano group is preferable. In (B2), the compound of the general formula (I) of the present invention is excluded.

The fourth component is a non-polar liquid crystal having a dielectric anisotropy of about 0, and is composed of compounds represented by the following formulas (C1) to (C3).

Embedded image In the above formula, R ^d and ^Pe each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch, and 3 to 6 May have a membered ring structure, and any -CH _2- present in the group is -O
-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF- or -C≡C- may be exchanged, and any hydrogen atom present in the group is fluorine. May be substituted by an atom or a trifluoromethoxy group, but may be a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, A straight-chain 3-alkenyl group, a straight-chain alkoxy group having 1 to 3 carbon atoms or a straight-chain alkyl group having 1 to 5 carbon atoms whose terminal is substituted by an alkoxy group having 1 to 3 carbon atoms is preferable, Further, at least one is a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms or a linear 3-alkenyl group having 4 to 7 carbon atoms. Particularly preferred.

Ring G, ring H, ring I and ring J are each independently
Trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or methyl groups, 1 Naphthalene-2,6-diyl group optionally substituted by two or more fluorine atoms, tetrahydronaphthalene-2,6 optionally substituted by one or two fluorine atoms
-Diyl group, 1,4-cyclohexenylene group optionally substituted by 1 to 2 fluorine atoms, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group Or a pyridine-2,5-diyl group, but in each compound, transdecahydronaphthalene-trans-2,6-diyl group, naphthalene which may be substituted with one or more fluorine atoms
-2,6-diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group is preferably one or less, the other ring is trans-1, It is preferably a 4-cyclohexylene group or a 1,4-phenylene group which may be substituted by one or two fluorine atoms or methyl groups.

L ^g , L ^h and L ⁱ are linking groups, each independently being a single bond, an ethylene group (—CH ₂ CH ₂ —), a 1,2-propylene group.
_{(-CH (CH 3) CH 2} - and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO
-, -OCO-, -OCF _2- , -CF ₂ O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF =
CF -, - C≡C- or represents a -CH = NN = CH-, a single bond, ethylene group, 1,4-butylene group, -COO -, - OCO -, - OCF 2 -, - CF 2 O -, -CF = CF
-, -C≡C- or -CH = NN = CH- is preferable, and at least one of them is (C2) and at least 2 is (C3).
Preferably, each represents a single bond. Further, the compound of the general formula (I) of the present invention is excluded from (C2).

The more preferable form of (C1) can be represented by the following general formulas (C1a) to (C1h).

Embedded image In each of the above formulas, R ^f and R ^g are each independently 1 to carbon atoms.
7 straight-chain alkyl group, linear 1-alkenyl group having 2 to 7 carbon atoms, linear 3-alkenyl group having 4 to 7 carbon atoms, linear alkoxy group having 1 to 3 carbon atoms Or the number of carbon atoms at the end
Represents a linear alkyl group having 1 to 5 carbon atoms substituted by an alkoxy group having 1 to 3 atoms, at least one of which is a linear alkyl group having 1 to 7 carbon atoms and a straight-chain alkyl group having 2 to 7 carbon atoms. Chain 1
Represents an alkenyl group or a linear 3-alkenyl group having 4 to 7 carbon atoms. However, when the rings G1 to G3 are aromatic rings, the corresponding R ^f is a ring H1 to
When the ring H3 is an aromatic ring, the corresponding R ^g excludes a 1-alkenyl group and an alkoxy group.

The ring G1 and the ring H1 are each independently trans
-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or methyl groups, 1 Naphthalene-2,6-diyl group optionally substituted by the above fluorine atom, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1 to 2 fluorine 1,4 optionally substituted by atoms
-Cyclohexenylene group, 1,3-dioxane-trans-2,5-
Diyl group, pyrimidine-2,5-diyl group or pyridine-2,5
-Diyl group, but in each compound, transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, 1-2 Tetrahydronaphthalene-2,6-diyl group which may be substituted by fluorine atoms, 1,4-cyclohexenylene group which may be substituted by fluorine atom,
1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,
It is preferred that the number of 5-diyl group or pyridine-2,5-diyl group is one or less, in which case the other ring is trans-1,4-
A cyclohexylene group or a 1,4-phenylene group which may be substituted by one or two fluorine atoms or a methyl group.

Ring G2 and ring H2 are each independently trans
-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or methyl groups, 1 Naphthalene-2,6-diyl group optionally substituted by the above fluorine atom, represents a tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, in each compound A transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, 1
It is preferable that the number of tetrahydronaphthalene-2,6-diyl groups which may be substituted by 2 to 2 fluorine atoms is one or less, and in that case, the other ring is a trans-1,4-cyclohexylene group or A 1,4-phenylene group which may be substituted by one or two fluorine atoms or a methyl group.

The ring G3 and the ring H3 are each independently a 1,4-phenylene group which may be substituted by 1 to 2 fluorine atoms or methyl groups, and may be substituted by one or more fluorine atoms. Naphthalene-2,6-diyl group, represents a tetrahydronaphthalene-2,6-diyl group which may be substituted by 1 to 2 fluorine atoms, but in each compound, is substituted by one or more fluorine atoms. Good naphthalene-
It is preferable that the number of 2,6-diyl groups and the number of tetrahydronaphthalene-2,6-diyl groups which may be substituted by one or two fluorine atoms be one or less.

A more preferred embodiment of (C2) can be represented by the following general formulas (C2a) to (C2m).

Embedded image In the above formula, ring G1, ring G2, ring G3, ring H1, ring H2 and ring H3 have the same meanings as described above, ring I1 is the same as ring G1, ring I2 is the same as ring G2, and ring I3 is the same as the ring G3. Represent meaning. In each of the above compounds,
Transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, may be substituted by 1 to 2 fluorine atoms Tetrahydronaphthalene-2,6-diyl group, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl Group or pyridine-2,5-diyl group is preferably one or less, in which case the other ring is substituted by trans-1,4-cyclohexylene group or one or two fluorine atoms or methyl groups A 1,4-phenylene group which may be

Next, more preferred embodiments of (C3) can be represented by the following general formulas (C3a) to (C3f).

Embedded image In the above formula, ring G1, ring G2, ring H1, ring H2, ring I1 and ring I2 have the same meanings as described above, ring J1 has the same meaning as ring G1 and ring J2 has the same meaning as ring G2. Further, in each of the above compounds, transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6- which may be substituted with one or more fluorine atoms.
Diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane -Trans-2,5-diyl group, pyrimidine
It is preferred that the number of -2,5-diyl groups or pyridine-2,5-diyl groups is one or less, in which case the other ring is trans-
A 1,4-cyclohexylene group or a 1,4-phenylene group which may be substituted by one or two fluorine atoms or methyl groups.

[0083]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Production of 2-propyl-7- (3,4,5-trifluorophenyl) -transtetradecahydrophenanthrene

Embedded image 41.6 g of magnesium was suspended in 40 mL of THF, and bromo-3,4,5-
A solution of 361 g of trifluorobenzene in 1.4 L of THF was added dropwise over about 1 hour at a speed at which THF was gently refluxed. After stirring for an additional hour, trans-7-propyl-trans-dodecahydrophenanthren-2-one 354 g (the preparation of this compound was obtained from D. Var.
ech, L. Lacombe and J. Lacques Nouv. J. Chim., 8, 4
45 (1984). ) Was added dropwise over 1 hour. After further stirring for 1 hour, 10% hydrochloric acid was added to stop the reaction. Ethyl acetate was added, the organic layer was separated, the aqueous layer was extracted with ethyl acetate, and the organic layers were combined. Water, saturated aqueous sodium bicarbonate,
The extract was washed with saturated saline and dried over anhydrous sodium sulfate.
After distilling off the solvent, 2.9 L of toluene and p-toluenesulfonic acid 1
Add 13.6 g of hydrate, and remove 1
The mixture was heated and stirred at 10 ° C. After the evaporation of water had ceased, the temperature was returned to room temperature, water was added, and the organic layer was separated. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, water and a saturated saline solution and dried over anhydrous sodium sulfate. Evaporate the solvent and dissolve the whole amount in 2 L of ethyl acetate,
52 g of 5% palladium / carbon (containing water) was added, and the mixture was stirred in an autoclave under a hydrogen pressure of 4 kg / cm ² . After stirring at room temperature for 5 hours, the catalyst was removed by filtration through Celite, and the solvent was distilled off. After evaporating the solvent, potassium-t-butoxide 16.5 in DMF 2.2 L under ice cooling
g, and then recrystallized from ethanol, and further recrystallized from ethanol to obtain 345 g of white crystals of 2-propyl-7- (3,4,5-trifluorophenyl) -transtetradecahydrophenanthrene. When the phase transition temperature was measured, it was transformed to an isotropic liquid phase at 106 ° C. when the temperature was raised from the crystal phase, and a nematic phase was shown at 73 ° C. or more during supercooling.

NMR: δ = 0.66 to 0.79 (m, 5H), δ = 0.82 to 1.3
5 (m, 15H), δ = 1.64 ~ 2.01 (m, 8H), δ = 2.47 (m, 1H), δ =
6.79 (dd, 2H, J = 6.4Hz, J = 9.2Hz) MS: m / e = 364 (M +)

The following compounds are obtained in the same manner. Trans-2-propyl-trans-7- (4-fluorophenyl) -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- (3,4-difluorophenyl) -trans-tetradecahydrophenanthrene trans- 2-propyl-trans-7- (3,5-difluorophenyl) -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- (4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans- 2-propyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- (4-difluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- (4-tri (Fluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- (4-chlorophenyl)-
Trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluoro-4 -
(Chlorophenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (4-fluorophenyl)-
Trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (3,4-difluorophenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (3,5-difluorophenyl)- Trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (3,4,5-trifluorophenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (4-trifluoromethoxy (Phenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (3 , 5-Difluoro-4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (4-difluorometh (Xyphenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (3-fluoro-4 -Trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl- Trans-7- (4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2-ethyl-trans- 7- (3,5-difluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene

Trans-2-butyl-trans-7- (4-fluorophenyl) -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- (3,4-difluorophenyl) -trans-tetradecahydro Phenanthrene trans-2-butyl-trans-7- (3,5-difluorophenyl) -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- (3,4,5-trifluorophenyl) -trans- Tetradecahydrophenanthrene trans-2-butyl-trans-7- (4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl ) -Trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-tetradecahydride Phenanthrene trans-2-butyl-trans-7- (4-difluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- (4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene Trans-2-butyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoro Methylphenyl) -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- (4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- (3-fluoro-4-chlorophenyl ) -Trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-tet Ladecahydrophenanthrene trans-2-pentyl-trans-7- (4-fluorophenyl) -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (3,4-difluorophenyl) -trans-tetradeca Hydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluorophenyl) -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (3,4,5-trifluorophenyl) -trans -Tetradecahydrophenanthrene trans-2-pentyl-trans-7- (4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (3-fluoro-4-trifluoromethoxy (Phenyl) -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (4-difluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (4-tri (Fluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (4-chlorophenyl)-
Trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluoro-4 -
(Chlorophenyl) -trans-tetradecahydrophenanthrene

Trans-2-hexyl-trans-7- (4-fluorophenyl) -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (3,4-difluorophenyl) -trans-tetradecahydro Phenanthrene trans-2-hexyl-trans-7- (3,5-difluorophenyl) -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (3,4,5-trifluorophenyl) -trans- Tetradecahydrophenanthrene trans-2-hexyl-trans-7- (4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl ) -Trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (4-difluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (4-tri (Fluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (4-chlorophenyl)-
Trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluoro-4 -
(Chlorophenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (4-fluorophenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (3,4-difluorophenyl) -Trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluorophenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (3,4,5-tri (Fluorophenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (3-fluoro- 4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluoro -4-
(Trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (4-difluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (4-tri (Fluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (4-chlorophenyl)-
Trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluoro-4 -
(Chlorophenyl) -trans-tetradecahydrophenanthrene

Example 2 Production of trans-2-propyl-trans-7- [2- (3,4,5-trifluorophenyl) ethyl] -trans-tetradecahydrophenanthrene

Embedded image Trans-7-propyl-trans-dodecahydrophenanthren-2-one is reacted with a Wittig reagent prepared from methoxymethyltriphenylphosphonium chloride and potassium-t-butoxide, and the resulting enol ether is added to a 10% aqueous hydrochloric acid solution in THF. After hydrolysis, isomerization was carried out with aqueous sodium hydroxide in methanol to give trans-7.
-Propyl-trans-tetradecahydrophenanthrene-
Get 2-carbaldehyde.

This was reacted again with a Wittig reagent prepared from methoxymethyltriphenylphosphonium chloride and potassium-t-butoxide, and the resulting enol ether was hydrolyzed with a 10% aqueous hydrochloric acid solution in THF to give (trans-7 -Propyl-trans-tetradecahydrophenanthren-2-yl) -acetaldehyde is obtained. to this,
After reacting a Grignard reactant prepared from bromo-3,4,5-trifluorobenzene and magnesium, dehydrated with p-toluenesulfonic acid monohydrate in toluene and trans-2-propyl-trans-7- After obtaining [2- (3,4,5-trifluorophenyl) vinyl] -trans-tetradecahydrophenanthrene, reduction is performed in the presence of a 5% palladium / carbon (water-containing) catalyst to give trans-2-propyl-trans. -7- [2-
(3,4,5-trifluorophenyl) ethyl] -trans-tetradecahydrophenanthrene was obtained.

The following compounds are obtained in the same manner. Trans-2-propyl-trans-7- [2- (4-fluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- [2- (3,4-difluorophenyl) ethyl ] -Trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- [2- (3,5-difluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- [2 -(4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- [2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl] -trans-tetradeca Hydrophenanthrene trans-2-propyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-propyl -Trans-7- [2- (4-trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- [2- (3-fluoro-4-trifluoromethylphenyl) Ethyl] -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- [2- (4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-propyl-trans -7- [2- (3-Fluoro-4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-propyl-trans-7- [2- (3,5-difluoro-
4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene

Trans-2-ethyl-trans-7- [2- (4-fluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2- (3,4-difluoro Phenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2- (3,5-difluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7 -[2- (3,4,5-trifluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl] -trans- Tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2 -(3,5-difluoro-4 -
Trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans -7- [2- (4-trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2- (3-fluoro-4-trifluoromethylphenyl) ethyl] -Trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2- (3,5-difluoro-4-
Trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2- (4-chlorophenyl)
Ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2- (3-fluoro-4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-ethyl-trans-7- [2- (3,5-difluoro-4-
Chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene

Trans-2-butyl-trans-7- [2- (4-fluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- [2- (3,4-difluoro Phenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- [2- (3,5-difluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7 -[2- (3,4,5-trifluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl] -trans- Tetradecahydrophenanthrene trans-2-butyl-trans-7- [2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- [2 -(3,5-difluoro-4 -
Trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans -7- [2- (4-trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- [2- (3-fluoro-4-trifluoromethylphenyl) ethyl] -Trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- [2- (3,5-difluoro-4-
Trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- [2- (4-chlorophenyl)
Ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- [2- (3-fluoro-4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-butyl-trans-7- [2- (3,5-difluoro-4-
Chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene

Trans-2-pentyl-trans-7- [2- (4-
Fluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- [2- (3,4-difluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans- 7- [2- (3,5-difluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- [2- (3,4,5-trifluorophenyl) ethyl] -trans -Tetradecahydrophenanthrene trans-2-pentyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- [2- (3 -Fluoro-4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl -Trans-7- [2- (4-trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- [2- (3-fluoro-4-trifluoromethylphenyl) Ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- [2- (4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans -7- [2- (3-Fluoro-4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-pentyl-trans-7- [2- (3,5-difluoro-
4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene

Trans-2-hexyl-trans-7- [2- (4-
Fluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- [2- (3,4-difluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans- 7- [2- (3,5-difluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- [2- (3,4,5-trifluorophenyl) ethyl] -trans -Tetradecahydrophenanthrene trans-2-hexyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- [2- (3 -Fluoro-4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl -Trans-7- [2- (4-trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- [2- (3-fluoro-4-trifluoromethylphenyl) Ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- [2- (4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans -7- [2- (3-Fluoro-4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-hexyl-trans-7- [2- (3,5-difluoro-
4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene

Trans-2-heptyl-trans-7- [2- (4-
Fluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- [2- (3,4-difluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans- 7- [2- (3,5-difluorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- [2- (3,4,5-trifluorophenyl) ethyl] -trans -Tetradecahydrophenanthrene trans-2-heptyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- [2- (3 -Fluoro-4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl -Trans-7- [2- (4-trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- [2- (3-fluoro-4-trifluoromethylphenyl) Ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethylphenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- [2- (4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans -7- [2- (3-Fluoro-4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene trans-2-heptyl-trans-7- [2- (3,5-difluoro-
4-chlorophenyl) ethyl] -trans-tetradecahydrophenanthrene

Example 3 Preparation of 2-fluoro-4- (trans-7-propyl-trans-tetradecahydrophenanthren-trans-2-yl) -benzonitrile

Embedded image Trans-7-propyl-trans-dodecahydrophenanthren-2-one with 2- (4-bromo-2-fluorophenyl) -4,4
After reacting a Grignard reagent prepared from -dimethyl-4,5-dihydrooxazole and magnesium, deprotection of the cyano group and dehydration of the aromatic ring with phosphorus oxychloride, followed by reduction in the presence of Raney nickel catalyst 2-Fluoro-4- (trans-7-propyl-trans-tetradecahydrophenanthren-trans-2-yl) -benzonitrile was obtained. When the phase transition temperature was measured,
When the temperature was raised from the crystal phase, the phase changed to an isotropic liquid phase at 173 ° C.

The following compounds are obtained in the same manner. 4- (trans-7-propyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (trans-7-ethyl-trans-tetradecahydrophenanthrene-trans-2-yl ) -Benzonitrile 4- (trans-7-ethyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (trans-7-butyl-trans-tetradecahydrophenanthrene-trans -2-yl) -benzonitrile 4- (trans-7-butyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (trans-7-pentyl-trans-tetradeca Hydrophenanthrene-trans-2-yl) -benzonitrile 4- (trans-7-pentyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (to 7-hexyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzonitrile 4- (trans-7-hexyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro -4- (trans-7-heptyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzonitrile 4- (trans-7-heptyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzo Nitrile

Example 4 2,6-Difluoro-4- (trans-
7-propyl-trans-tetradecahydrophenanthrene
-Trans-2-yl) -benzonitrile

Embedded image After the trans-2-propyl-trans-7- (3,5-difluorophenyl) -trans-tetradecahydrophenanthrene produced by the method of Example 1 was lithiated with a butyllithium-hexane solution, carbon gas was removed. The reaction gives 2,5-difluoro-4- (trans-7-propyl-trans-tetradecahydrophenanthren-trans-2-yl) -benzoic acid. This was converted to an acid chloride with thionyl chloride and then reacted with ammonia to obtain 2,5-difluoro-4- (trans-7-propyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzamide. . This is reacted with phosphorus oxychloride and dehydrated to give 2,5-difluoro
-4- (Trans-7-propyl-trans-tetradecahydrophenanthren-trans-2-yl) -benzonitrile was obtained.

The following compounds are obtained in the same manner. 2,6-difluoro-4- (trans-7-ethyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (trans-7-butyl-trans-tetradeca Hydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (trans-7-pentyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4 -(Trans-7-hexyl-trans-tetradecahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (trans-7-heptyl-trans-tetradecahydrophenanthrene-trans-2- Yl) -benzonitrile

Example 5 trans-7-propyl-trans-tetradecahydrophenanthrene-2-carboxylic acid 4-
Production of cyano-3-fluorophenyl

Embedded image Trans-7-propyl-trans-tetradecahydrophenanthrene-2-carbaldehyde prepared in Example 2 was oxidized with silver oxide adjusted from silver nitrate and sodium hydroxide, and trans-7-propyl-trans-tetradecahydro Phenanthrene-2-carboxylic acid is obtained. This was converted to an acid chloride with thionyl chloride, and then reacted with 2-fluoro-4-hydroxybenzonitrile to give trans-7-propyl-trans-tetradecahydrophenanthrene-2-carboxylic acid 4-cyano-3-fluoro acid Obtain phenyl.

The following compounds are obtained in the same manner. Trans-7-propyl-trans-tetradecahydrophenanthrene-2-carboxylic acid 4-cyanophenyl trans-7-propyl-trans-tetradecahydrophenanthrene-2-carboxylic acid 4-cyano-3,5-difluorophenyl trans- 7-ethyl-trans-tetradecahydrophenanthrene-2-carboxylic acid 4-cyanophenyl trans-7-ethyl-trans-tetradecahydrophenanthrene-2-carboxylic acid 4-cyano-3-fluorophenyl trans-7-ethyl- Trans-tetradecahydrophenanthrene-2-carboxylic acid 4-cyano-3,5-difluorophenyl trans-7-butyl-trans-tetradecahydrophenanthrene-2-carboxylic acid 4-cyanophenyl trans-7-butyl-trans- Tetradecahydrophenanthrene-2-carboxylic acid 4-cyano-3-fluorophenyl trans-7-butyl-trans-tetra Ladecahydrophenanthrene-2-carboxylate 4-cyano-3,5-difluorophenyl trans-7-pentyl-trans-tetradecahydrophenanthrene-2-carboxylate 4-cyanophenyl trans-7-pentyl-trans-tetradeca 4-Cyano-3-fluorophenyl trans-7-pentyl-trans-tetradecahydrophenanthrene-2-carboxylate 4-cyano-3,5-difluorophenyl trans-7-pentyl-trans-tetradecahydrophenanthrene-2-carboxylate 4-cyanophenyl tetradecahydrophenanthrene-2-carboxylate trans-7-pentyl-trans-tetradecahydrophenanthrene-2-carboxylate 4-cyano-3-fluorophenyl trans-7-pentyl-trans-tetradecahydrophenanthrene 4-Cyano-3,5-difluorophenyl-2-carboxylate trans-7-heptyl-trans-tetradecahi Lophenanthrene-2-carboxylate 4-cyanophenyl trans-7-heptyl-trans-tetradecahydrophenanthrene-2-carboxylate 4-cyano-3-fluorophenyl trans-7-heptyl-trans-tetradecahydrophenanthrene-2 -Carboxylic acid 4-cyano-3,5-difluorophenyl

Example 6 Preparation of trans-2- (3,4,5-trifluorophenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene

Embedded image Trans-dodecahydrophenanthrene-2,7-dione monoethylene acetal is reacted with a Grignard reagent prepared from bromo-3,4,5-trifluorobenzene and magnesium, and then p-toluenesulfonic acid monohydrate in toluene De-7- (3,4,5-trifluorophenyl) -3,4,4a, 4b, 5,6,8a, 9,10,10a-trans-dodecahydro-1H-phenanthrene-2 -One ethylene acetal and trans-7- (3,4,5-trifluorophenyl) -3,4,4a, 4b,
After obtaining a mixture of 5,8,8a, 9,10,10a-trans-dodecahydro-1H-phenanthren-2-one ethylene acetal, 5
Trans-7- (3,4,5-trifluorophenyl) -trans-
Dodecahydrophenanthrene-2-one ethylene acetal was obtained. After removing the protecting group of the carbonyl group, methoxymethyltriphenylphosphonium chloride and potassium-t
-Wittig reagent prepared from -butoxide is reacted, and the resulting enol ether is hydrolyzed with a 10% hydrochloric acid aqueous solution in THF, and then trans-7- (3,4, 5-trifluorophenyl) -trans-tetrahydrophenanthrene-trans
2-carbaldehyde was obtained. By reacting this with a Wittig reagent prepared from methyltriphenylphosphonium bromide and potassium-t-butoxide,
Trans-2- (3,4,5-trifluorophenyl) -trans-7
-Vinyl-trans-tetrahydrophenanthrene is obtained.

Trans-7- (3,4,5-trifluorophenyl) -trans-tetrahydrophenanthrene-trans-2
-The following compounds are obtained by reacting carbaldehyde with various Wittig reagents. Trans-2- (4-fluorophenyl) -trans-7-vinyl-
Trans-tetrahydrophenanthrene trans-2- (3,4-difluorophenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3,5-difluorophenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene Trans-2- (4-trifluoromethoxyphenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3-fluoro-4-trifluoromethoxyphenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene Trans-2- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (4-difluoromethoxyphenyl) -trans
-7-vinyl-trans-tetrahydrophenanthrene trans-2- (4-trifluoromethylphenyl) -trans
-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3-fluoro-4-trifluoromethylphenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3,5-difluoro-4-tri (Fluoromethylphenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (4-chlorophenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3-fluoro-4-chlorophenyl) -trans -
7-vinyl-trans-tetrahydrophenanthrene trans-2- (3,5-difluoro-4-chlorophenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene

Trans-2- (trans-1-propenyl) -trans-7- (4-fluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3 ,Four
-Difluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3,5
-Difluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3,
4,5-trifluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (4-
(Trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3-
(Fluoro-4-trifluoromethoxyphenyl) -trans-
Tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (4-
Difluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (4-
(Trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3-
Fluoro-4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethylphenyl) -trans
-Tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (4-
(Chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3-
Fluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3,5
-Difluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene

Trans-2- (trans-1-butenyl) -trans-7- (4-fluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3 ,Four-
Difluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3,5-
Difluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3,4,5
-Trifluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans- 1-butenyl) -trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3,5-
Difluoro-4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (4-difluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (Trans-1-butenyl) -trans-7- (4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3-fluoro-4- (Trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3,5-
Difluoro-4-trifluoromethylphenyl) -trans-
Tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3 -Fluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3,5-
Difluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene

Trans-2- (trans-1-pentenyl) -trans-7- (4-fluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3 ,Four
-Difluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3,5
-Difluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3,
4,5-trifluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (4-
(Trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3-
(Fluoro-4-trifluoromethoxyphenyl) -trans-
Tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (4-
Difluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (4-
(Trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3-
Fluoro-4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethylphenyl) -trans
-Tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (4-
(Chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3-
Fluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3,5
-Difluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (4-
(Fluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,4
-Difluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,5
-Difluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,
4,5-trifluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (4-
(Trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3-
(Fluoro-4-trifluoromethoxyphenyl) -trans-
Tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (4-
Difluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (4-
(Trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3-
Fluoro-4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethylphenyl) -trans
-Tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (4-
(Chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3-
Fluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,5
-Difluoro-4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -trans-7- (4-fluorophenyl) -trans-tetradecahydrophenanthrene

Trans-2- (3-butenyl) -trans-7- (3,
4-difluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3,5-difluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -Trans-7- (3,4,5-trifluorophenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -trans-7- (4-trifluoromethoxyphenyl) -trans-tetradeca Hydrophenanthrene trans-2- (3-butenyl) -trans-7- (3-fluoro-4-
(Trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3,5-difluoro
-4-trifluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -trans-7- (4-difluoromethoxyphenyl) -trans-tetradecahydrophenanthrene trans-2- (3- (Butenyl) -trans-7- (4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3-fluoro-4-
(Trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3,5-difluoro
-4-trifluoromethylphenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -trans-7- (4-chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -Trans-7- (3-fluoro-4-
(Chlorophenyl) -trans-tetradecahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3,5-difluoro
-4-chlorophenyl) -trans-tetradecahydrophenanthrene

Example 7 trans-2-propyl-7- (3,4,
5-triphenyl) -trans-1,2,3,4,4a, 9,10,10a-
Production of octahydrophenanthrene

Embedded image 7-methoxy-trans-2-propyl-trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 20 g (The preparation of this compound is described in D. Varech, L. Lacombe and J. Lacques N
ouv. J. Chim., 8, 445 (1984). ) Was refluxed with 80 mL of acetic acid 80 mL and 80 mL of 40% hydrobromic acid for 10 hours, and trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthren-2-ol 19.1 g I got The crude product was dissolved in methylene chloride (100 mL), trifluoromethanesulfonic anhydride (15.8 mL) was added and suspended, and the mixture was cooled to 5 ° C. With vigorous stirring, 15 mL of pyridine is added dropwise.
Stir for 1 hour. The reaction was stopped by adding 100 mL of water, and the organic layer was separated. The aqueous layer was extracted with 80 mL of dichloromethane,
The organic layers were combined, washed with diluted hydrochloric acid, a saturated aqueous solution of sodium bicarbonate, water and then a saturated saline solution, and dried and dried over anhydrous sodium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane) to give trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-2 trifluoromethanesulfonate. -I got 24.5g of il. to this,
13.4 g of 3,4,5-trifluorophenylboric acid (this is 3,3
It was obtained by reacting a Grignard reagent prepared from 4,5-trifluorobromobenzene and magnesium with trimethylboric acid, and then hydrolyzing with dilute hydrochloric acid. ) And tetrakis (triphenylphosphine) palladium (0) 1.5
g, and potassium phosphate 21.2 g with dimethylformamide
Stirred at 80 ° C. in 120 mL for 10 hours. Thereafter, the mixture was cooled to room temperature, water was added, and the mixture was extracted with toluene. The organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. The crude product obtained by evaporating the solvent was purified by silica gel column chromatography (hexane), and further recrystallized three times from ethanol to give trans-2-propyl-7- (3,
(4,5-trifluphenyl) -trans-1,2,3,4,4a, 9,10,10a
-6.3 g of octahydrophenanthrene was obtained.

NMR: δ = 0.86 to 0.89 (m, 5H), δ = 1.11 to 1.3
5 (m, 15H), δ = 1.74 to 1.86 (m, 8H), δ = 2.37 (m, 1H), δ =
6.79 (dd, 2H, J = 6.4Hz, J = 9.2Hz) MS: m / e = 358 (M +)

In the same manner, the following compound is obtained. Trans-2-propyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (3 , 4-Difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluorophenyl) -trans-1 , 2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9 , 10,10a-Octahydrophenanthrene trans-2-propyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans- 2-propyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (3 -Fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-Octahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (4-chlorophenyl)-
Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4 , 4a, 9,10,10a-Octahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluoro-4-
(Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

Trans-2-ethyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7 -(3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (3,5-difluorophenyl)- Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (3,4,5-trifluorophenyl) -trans-1,2,3 , 4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a -Octahydrophenanthrene trans-2-ethyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene trans-2-ethyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2- Ethyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (3-fluoro -4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene trans-2-ethyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl- Trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (3,5- Difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

Trans-2-butyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7 -(3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluorophenyl)- Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (3,4,5-trifluorophenyl) -trans-1,2,3 , 4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a -Octahydrophenanthrene trans-2-butyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2- Butyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (3-fluoro -4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene trans-2-butyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl- Trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (3,5- Difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

Trans-2-pentyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7 -(3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluorophenyl)- Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (3,4,5-trifluorophenyl) -trans-1,2,3 , 4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a -Octahydrophenanthrene trans-2-pentyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans- 2-pentyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (3 -Fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-Octahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (4-chlorophenyl)-
Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4 , 4a, 9,10,10a-Octahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluoro-4-
(Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

Trans-2-hexyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7 -(3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluorophenyl)- Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (3,4,5-trifluorophenyl) -trans-1,2,3 , 4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a -Octahydrophenanthrene trans-2-hexyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans- 2-hexyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (3 -Fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (4-chlorophenyl)-
Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4 , 4a, 9,10,10a-Octahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluoro-4-
(Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

Trans-2-heptyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7 -(3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluorophenyl)- Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (3,4,5-trifluorophenyl) -trans-1,2,3 , 4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a -Octahydrophenanthrene trans-2-heptyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans- 2-heptyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (3 -Fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (4-chlorophenyl)-
Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4 , 4a, 9,10,10a-Octahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluoro-4-
(Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

Example 8 trans-2-propyl-7- (3,4-
Difluorophenylethynyl) -trans-1,2,3,4,4a, 9,
Production of 10,10a-octahydrophenanthrene

Embedded image Trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthren-2-yl in the presence of tetrakis (triphenylphosphine) palladium (0) in dimethylformamide and triethylamine 4 -Ethynyl-1,2-difluorobenzene was reacted, purified by silica gel column chromatography (hexane), and further recrystallized from ethanol to give trans-2-propyl-7- (3,4-difluorophenylethynyl)- Transformer-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene was obtained.

In the same manner, the following compound is obtained. Trans-2-propyl-trans-7- (4-fluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- ( 3,4-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluorophenylethynyl)- Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (4-trifluoromethoxyphenylethynyl) -trans-1,2,3,4 , 4a, 9,10,10a
-Octahydrophenanthrene trans-2-propyl-trans-7- (3-fluoro-4-trifluoromethoxyphenylethynyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenylethynyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (4-difluoromethoxyphenylethynyl) -trans-1,2,3,4,4a, 9, 10,10a-
Octahydrophenanthrene trans-2-propyl-trans-7- (4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-propyl-trans-7- (3-fluoro-4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenylethynyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-propyl-trans-7- (4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a- Octahydrophenanthrene trans-2-propyl-trans-7- (3-fluoro-4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluoro-4-
(Chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene

Trans-2-ethyl-trans-7- (4-fluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-ethyl-trans-7- (3,4-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl- Trans-7- (3,5-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (3,4, 5-trifluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (4-trifluoromethoxyphenylethynyl) -trans -1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-ethyl-trans-7- (3-fluoro-4-trifluoromethoxyphenylethynyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene trans-2-ethyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenylethynyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (4-difluoromethoxyphenylethynyl) -trans-1,2,3,4,4a, 9,10, 10a-octahydrophenanthrene trans-2-ethyl-trans-7- (4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2- Ethyl-trans-7- (3-fluoro-4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (3,5-difluoro-4-trifluoromethylphenylethynyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans-7- (4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydro Phenanthrene trans-2-ethyl-trans-7- (3-fluoro-4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-ethyl-trans -7- (3,5-difluoro-4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene

Trans-2-butyl-trans-7- (4-fluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-butyl-trans-7- (3,4-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl- Trans-7- (3,5-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (3,4, 5-trifluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (4-trifluoromethoxyphenylethynyl) -trans -1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-butyl-trans-7- (3-fluoro-4-trifluoromethoxyphenylethynyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenylethynyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (4-difluoromethoxyphenylethynyl) -trans-1,2,3,4,4a, 9,10, 10a-octahydrophenanthrene trans-2-butyl-trans-7- (4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2- Butyl-trans-7- (3-fluoro-4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoromethylphenylethynyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans-7- (4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydro Phenanthrene trans-2-butyl-trans-7- (3-fluoro-4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-butyl-trans -7- (3,5-difluoro-4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene

Trans-2-pentyl-trans-7- (4-fluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene trans-2-pentyl-trans-7- (3,4-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl -Trans-7- (3,5-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (3,4 , 5-trifluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (4-trifluoromethoxyphenylethynyl)- Transformer-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene trans-2-pentyl-trans-7- (3-fluoro-4-trifluoromethoxyphenylethynyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenylethynyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (4-difluoromethoxyphenylethynyl) -trans-1,2,3,4,4a, 9, 10,10a-
Octahydrophenanthrene trans-2-pentyl-trans-7- (4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-pentyl-trans-7- (3-fluoro-4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenylethynyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-pentyl-trans-7- (4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a- Octahydrophenanthrene trans-2-pentyl-trans-7- (3-fluoro-4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluoro-4-
(Chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene

Trans-2-hexyl-trans-7- (4-fluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene trans-2-hexyl-trans-7- (3,4-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl -Trans-7- (3,5-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (3,4 , 5-trifluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (4-trifluoromethoxyphenylethynyl)- Transformer-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene trans-2-hexyl-trans-7- (3-fluoro-4-trifluoromethoxyphenylethynyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenylethynyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (4-difluoromethoxyphenylethynyl) -trans-1,2,3,4,4a, 9, 10,10a-
Octahydrophenanthrene trans-2-hexyl-trans-7- (4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-hexyl-trans-7- (3-fluoro-4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenylethynyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-hexyl-trans-7- (4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a- Octahydrophenanthrene trans-2-hexyl-trans-7- (3-fluoro-4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluoro-4-
(Chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene

Trans-2-heptyl-trans-7- (4-fluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene trans-2-heptyl-trans-7- (3,4-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl -Trans-7- (3,5-difluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (3,4 , 5-trifluorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (4-trifluoromethoxyphenylethynyl)- Transformer-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene trans-2-heptyl-trans-7- (3-fluoro-4-trifluoromethoxyphenylethynyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluoro-4-
(Trifluoromethoxyphenylethynyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (4-difluoromethoxyphenylethynyl) -trans-1,2,3,4,4a, 9, 10,10a-
Octahydrophenanthrene trans-2-heptyl-trans-7- (4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-heptyl-trans-7- (3-fluoro-4-trifluoromethylphenylethynyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluoro-4-
(Trifluoromethylphenylethynyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene trans-2-heptyl-trans-7- (4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a- Octahydrophenanthrene trans-2-heptyl-trans-7- (3-fluoro-4-chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluoro-4-
(Chlorophenylethynyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene

Example 9 8-Fluoro-trans-2-propyl-7- (3,4,5-trifluorophenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene and 6-fluoro-trans-2-propyl-7- (3,4,5-trifluorophenyl) -trans-1,2,3,4, Production of 4a, 9,10,10a-octahydrophenanthrene

Embedded image Trans-7-propyl-trans-4b obtained in Example 7,
5,6,7,8,8a, 9,10-Octahydrophenanthren-2-ol in methylene chloride, bistetrafluoroborate N, N'-
Difluoro-2,2'-bipyridinium (MEC-31) was gradually added, and the mixture was further stirred at room temperature for 5 hours. Water and then a 10% aqueous sodium hydroxide solution are added to decompose excess fluorinating agent,
After returning to acidic with diluted hydrochloric acid, the organic layer was separated. The aqueous layer was extracted with dichloromethane, and the organic layers were combined, washed with water and then with a saturated saline solution, and dried and dried over anhydrous sodium sulfate.
The crude product obtained by evaporating the solvent was separated and purified by silica gel column chromatography (hexane and toluene), and 8-fluoro-trans-7-propyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthren-2-ol and 6-fluoro-trans-7-propyl-trans-4b, 5,6,
Each of 7,8,8a, 9,10-octahydrophenanthren-2-ol was obtained.

The obtained 8-fluoro-trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthren-2-ol was dissolved in methylene chloride and dried. Trifluoromethanesulfonic acid was added and suspended, and cooled to 5 ° C. With vigorous stirring, pyridine was added dropwise for another 1 hour.
Stirred for hours. Water was added to stop the reaction, and the organic layer was separated. The aqueous layer was extracted with dichloromethane, and the organic layers were combined, washed with diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate, water, and then with saturated saline, and dried over anhydrous sodium sulfate and dried. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane) to give 8-fluoro-trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10-octafluoromethanesulfonic acid. Hydrophenanthren-2-yl was obtained. In addition, 3,4,5
-Trifluorophenylboric acid (This is obtained by reacting a Grignard reagent prepared from 3,4,5-trifluorobromobenzene and magnesium with trimethylboric acid, followed by hydrolysis with dilute hydrochloric acid. ), Tetrakis (triphenylphosphine) palladium (0), and potassium phosphate were stirred at 80 ° C. for 10 hours in dimethylformamide. Thereafter, the mixture was cooled to room temperature, water was added, and the mixture was extracted with toluene. The organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. The crude product obtained by evaporating the solvent was purified by silica gel column chromatography (hexane), and further recrystallized three times from ethanol to give 8-fluoro-trans-2-propyl-7- (3,4 , 5-trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene was obtained. 6-fluoro-isolated
Trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthren-2-ol was prepared in the same manner as above.
-Fluoro-trans-2-propyl-7- (3,4,5-trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene was obtained.

In the same manner, the following compound is obtained. 8-fluoro-trans-2-propyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2- Propyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (4-trifluoromethoxy Phenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-
1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4 , 4a, 9,10,1
0a-octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9 , 10,10a-Octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 8-fluoro-trans-2-propyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene

8-Fluoro-trans-2-ethyl-trans-
7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8 -Fluoro-trans-2-ethyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2 -Ethyl-trans-7- (3,4,5-trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a , 9,10,10a-Octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10 , 10a-Octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene 8-fluoro-trans-2-ethyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene

8-Fluoro-trans-2-butyl-trans-
7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8 -Fluoro-trans-2-butyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2 -Butyl-trans-7- (3,4,5-trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a , 9,10,10a-Octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,
3,4,4a, 9,10,10a-Octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10 , 10a-Octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene 8-fluoro-trans-2-butyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene

8-Fluoro-trans-2-pentyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydro Phenanthrene 8-fluoro-trans-2-pentyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans -2-pentyl-trans-7- (3,4,5-
(Trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-
1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4 , 4a, 9,10,1
0a-octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9 , 10,10a-Octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 8-fluoro-trans-2-pentyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene

8-Fluoro-trans-2-hexyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydro Phenanthrene 8-fluoro-trans-2-hexyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans -2-hexyl-trans-7- (3,4,5-
(Trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-
1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4 , 4a, 9,10,1
0a-octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9 , 10,10a-Octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 8-fluoro-trans-2-hexyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene

8-Fluoro-trans-2-heptyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydro Phenanthrene 8-fluoro-trans-2-heptyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans -2-heptyl-trans-7- (3,4,5-
(Trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-
1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4 , 4a, 9,10,1
0a-octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9 , 10,10a-Octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 8-fluoro-trans-2-heptyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene

6-fluoro-trans-2-propyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6-fluoro-trans-2-propyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydro Phenanthrene 6-fluoro-trans-2-propyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans -2-propyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6-fluoro-trans-2-propyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-propyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-
1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-propyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4 , 4a, 9,10,1
0a-octahydrophenanthrene 6-fluoro-trans-2-propyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 6-fluoro-trans-2-propyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-propyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-propyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9 , 10,10a-Octahydrophenanthrene 6-fluoro-trans-2-propyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 6-fluoro-trans-2-propyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene

6-fluoro-trans-2-ethyl-trans-
7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6 -Fluoro-trans-2-ethyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2 -Ethyl-trans-7- (3,4,5-trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a , 9,10,10a
-Octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10 , 10a-Octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene 6-fluoro-trans-2-ethyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene

6-fluoro-trans-2-butyl-trans-
7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6 -Fluoro-trans-2-butyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2 -Butyl-trans-7- (3,4,5-trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a , 9,10,10a
-Octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10 , 10a-Octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene 6-fluoro-trans-2-butyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene

6-fluoro-trans-2-pentyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydro Phenanthrene 6-fluoro-trans-2-pentyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans -2-pentyl-trans-7- (3,4,5-
(Trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-
1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4 , 4a, 9,10,1
0a-octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9 , 10,10a-Octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 6-fluoro-trans-2-pentyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene

6-fluoro-trans-2-hexyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydro Phenanthrene 6-fluoro-trans-2-hexyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans -2-hexyl-trans-7- (3,4,5-
(Trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-
1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4 , 4a, 9,10,1
0a-octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9 , 10,10a-Octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 6-fluoro-trans-2-hexyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene

6-fluoro-trans-2-heptyl-trans-7- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydro Phenanthrene 6-fluoro-trans-2-heptyl-trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans -2-heptyl-trans-7- (3,4,5-
(Trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-
1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (4-difluoromethoxyphenyl) -trans-1,2,3,4 , 4a, 9,10,1
0a-octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,1
0a-octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -trans-1,
2,3,4,4a, 9,10,10a-octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (4-chlorophenyl) -trans-1,2,3,4,4a, 9 , 10,10a-Octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene 6-fluoro-trans-2-heptyl-trans-7- (3,5-difluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene

Example 10 trans-2-propyl-7- (3,
(4,5-trifluorophenyl) -trans-1,2,3,4,4a, 9,1
Production of 0,10a-octahydrophenanthrene

Embedded image (3,5-Difluorophenyl) -acetic acid was converted to acid chloride with thionyl chloride, and then reacted with ethylene gas at -10 ° C in the presence of aluminum chloride in methylene chloride to give 5,7-difluoro-3,4-dihydrochloride. -1H-Naphthalen-2-one is obtained. To this was added pyrrolidine in toluene and heated for 3 hours to remove azeotropic water. Excess pyrrolidine was removed by azeotropic distillation with toluene to obtain 1- (5,7-difluoro-1,4-dihydronaphthalen-2-yl) -pyrrolidine. The mixture was cooled to room temperature, toluene was added again, and methyl vinyl ketone was added dropwise at 25 ° C. or lower over 1 hour while cooling with a water bath. Immediately after completion of the dropwise addition, the mixture was heated and refluxed for 20 hours. After cooling to room temperature, a pH 5 buffer solution prepared with sodium acetate, acetic acid and water was added, and the mixture was further heated under reflux for 4 hours. After cooling to room temperature, the organic layer was separated and washed with water and saturated saline. After drying over anhydrous sodium sulfate and evaporating the solvent, 6,8-difluoro-trans-4,4a, 9,10-tetrahydro
-3H-phenanthren-2-one was obtained.

At -40 ° C. or lower, metallic lithium in liquid ammonia was added little by little and dissolved. While maintaining the internal temperature at -30 to -40 ° C, the T of 6,8-difluoro-trans-4,4a, 9,10-tetrahydro-3H-phenanthren-2-one and t-butanol
The HF solution was added dropwise, and after the addition, stirring was continued for 30 minutes. After lithium ammonium was oxidized by adding solid ammonium chloride little by little, the temperature was raised to room temperature, and ammonia was distilled off. Add water, extract with toluene, wash the organic layer with saturated saline,
After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain 6,8-difluoro-trans-3,4,4a, 9,10,10a-hexahydro-1H-phenanthren-2-one.

This was reacted with a Wittig reagent prepared from methoxymethyltriphenylphosphonium chloride and potassium-t-butoxide, and the resulting enol ether was hydrolyzed with a 10% aqueous hydrochloric acid solution in THF, and then hydrolyzed in methanol. Isomerization was performed with a sodium aqueous solution to obtain 6,8-difluoro-trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene-trans-2-carbaldehyde.

By reacting ethyltriphenylphosphonium bromide with a Wittig reagent prepared from potassium-t-butoxide, 6,8-difluoro
-Trans-2-propenyl-trans-1,2,3,4,4a, 9,10,10
After obtaining a-octahydrophenanthrene, 5% palladium
/ 6,8 by reduction with hydrogen in the presence of carbon (hydrous) catalyst
-Difluoro-trans-2-propyl-trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene is obtained. This is n
After lithiation with -butyllithium-hexane solution,
Reaction of iodine with 6,8-difluoro-7-iodo-trans-2
-Propyl-trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene is obtained.

6,4,5-Difluoro-7-iodo-trans-2-propyl-trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene with 3,4,5-trifluorophenyl Boric acid (obtained by reacting a Grignard reagent prepared from 3,4,5-trifluorobromobenzene and magnesium with trimethyl boric acid and then hydrolyzing with dilute hydrochloric acid) and tetrakis (Triphenylphosphine) palladium (0) and potassium phosphate were added, and the mixture was stirred in dimethylformamide at 80 ° C for 10 hours. Thereafter, the mixture was cooled to room temperature, water was added, and the mixture was extracted with toluene. The organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate.
The crude product obtained by evaporating the solvent was purified by silica gel column chromatography (hexane), and further recrystallized three times from ethanol to give 6,8-difluoro-trans-2-propyl-7- (3 , 4,5-trifluorophenyl) -trans-1,
2,3,4,4a, 9,10,10a-Octahydrophenanthrene was obtained.

The following compounds are obtained in the same manner. 6,8-difluoro-trans-2-propyl- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- Propyl- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-propyl- (3,5-difluoro Phenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-propyl- (4-trifluoromethoxyphenyl) -trans-1,2 , 3,4,4a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2-propyl- (3-fluoro-4-
(Trifluoromethoxyphenyl) -trans-1,2,3,4,4a,
9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2-propyl- (3,5-difluoro
-4-trifluoromethoxyphenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-propyl- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octa Hydrophenanthrene 6,8-difluoro-trans-2-propyl- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro- Trans-2-propyl- (3-fluoro-4-
(Trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-propyl- (3,5-difluoro
-4-trifluoromethylphenyl) -trans-1,2,3,4,4
a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-propyl- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-propyl- (3-fluoro-4-
(Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-propyl- (3,5-difluoro
-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

6,8-difluoro-trans-2-ethyl- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans -2-ethyl- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-ethyl- (3, 5-Difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-ethyl- (3,4,5-trifluorophenyl) -Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-ethyl- (4-trifluoromethoxyphenyl) -trans-1,2,3 , 4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-ethyl- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a , 9,
10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-ethyl- (3,5-difluoro-4
-Trifluoromethoxyphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2-ethyl- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octa Hydrophenanthrene 6,8-difluoro-trans-2-ethyl- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro- Trans-2-ethyl- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6,8-difluoro-trans-2-ethyl- (3,5-difluoro-4
-Trifluoromethylphenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-ethyl- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6, 8-difluoro-trans-2-ethyl- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2 -Ethyl- (3,5-difluoro-4
-Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

6,8-difluoro-trans-2-butyl- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans -2-butyl- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-butyl- (3, 5-Difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-butyl- (3,4,5-trifluorophenyl) -Trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-butyl- (4-trifluoromethoxyphenyl) -trans-1,2,3 , 4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-butyl- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a , 9,
10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-butyl- (3,5-difluoro-4
-Trifluoromethoxyphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2-butyl- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octa Hydrophenanthrene 6,8-difluoro-trans-2-butyl- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro- Trans-2-butyl- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6,8-difluoro-trans-2-butyl- (3,5-difluoro-4
-Trifluoromethylphenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-butyl- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6, 8-difluoro-trans-2-butyl- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2 -Butyl- (3,5-difluoro-4
-Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

6,8-difluoro-trans-2-pentyl- (4-
(Fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-pentyl- (3,4-difluorophenyl) -trans-1, 2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-pentyl- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-pentyl- (3,4,5-trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a -Octahydrophenanthrene 6,8-difluoro-trans-2-pentyl- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8- Difluoro-trans-2-pentyl- (3-fluoro-4-
(Trifluoromethoxyphenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-pentyl- (3,5-difluoro
-4-trifluoromethoxyphenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-pentyl- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octa Hydrophenanthrene 6,8-difluoro-trans-2-pentyl- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro- Trans-2-pentyl- (3-fluoro-4-
(Trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-pentyl- (3,5-difluoro
-4-trifluoromethylphenyl) -trans-1,2,3,4,4
a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-pentyl- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-pentyl- (3-fluoro-4-
(Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-pentyl- (3,5-difluoro
-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

6,8-Difluoro-trans-2-hexyl- (4-
(Fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-hexyl- (3,4-difluorophenyl) -trans-1, 2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-hexyl- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-hexyl- (3,4,5-trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a -Octahydrophenanthrene 6,8-difluoro-trans-2-hexyl- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8- Difluoro-trans-2-hexyl- (3-fluoro-4-
(Trifluoromethoxyphenyl) -trans-1,2,3,4,4a,
9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2-hexyl- (3,5-difluoro
-4-trifluoromethoxyphenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-hexyl- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octa Hydrophenanthrene 6,8-difluoro-trans-2-hexyl- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro- Trans-2-hexyl- (3-fluoro-4-
(Trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-hexyl- (3,5-difluoro
-4-trifluoromethylphenyl) -trans-1,2,3,4,4
a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-hexyl- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-hexyl- (3-fluoro-4-
(Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-hexyl- (3,5-difluoro
-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

6,8-Difluoro-trans-2-heptyl- (4-
(Fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-heptyl- (3,4-difluorophenyl) -trans-1, 2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-heptyl- (3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-heptyl- (3,4,5-trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a -Octahydrophenanthrene 6,8-difluoro-trans-2-heptyl- (4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8- Difluoro-trans-2-heptyl- (3-fluoro-4-
(Trifluoromethoxyphenyl) -trans-1,2,3,4,4a,
9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2-heptyl- (3,5-difluoro
-4-trifluoromethoxyphenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-heptyl- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octa Hydrophenanthrene 6,8-difluoro-trans-2-heptyl- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro- Trans-2-heptyl- (3-fluoro-4-
(Trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-heptyl- (3,5-difluoro
-4-trifluoromethylphenyl) -trans-1,2,3,4,4
a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-heptyl- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-heptyl- (3-fluoro-4-
(Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-heptyl- (3,5-difluoro
-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

6,8-difluoro-trans-1,2,3,4,4a, 9,1
By reacting various Wittig reagents with 0,10a-octahydrophenanthrene-trans-2-carbaldehyde and then performing the same reaction, the following compounds are obtained. 6,8-difluoro-trans-2-vinyl- (4-fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- Vinyl- (3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-vinyl- (3,5-difluoro Phenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-vinyl- (3,4,5-trifluorophenyl) -trans- 1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-vinyl- (4-trifluoromethoxyphenyl) -trans-1,2,3,4, 4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-vinyl- (3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-vinyl- (3,5-difluoro-4
-Trifluoromethoxyphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2-vinyl- (4-difluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octa Hydrophenanthrene 6,8-difluoro-trans-2-vinyl- (4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro- Trans-2-vinyl- (3-fluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,1
0,10a-octahydrophenanthrene 6,8-difluoro-trans-2-vinyl- (3,5-difluoro-4
-Trifluoromethylphenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2-vinyl- (4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6, 8-difluoro-trans-2-vinyl- (3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2 -Vinyl- (3,5-difluoro-4
-Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene

6,8-difluoro-trans-2- (trans-1-
(Propenyl)-(4-fluorophenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl)-
(3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl)-
(3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl)-
(3,4,5-trifluorophenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl)-
(4-trifluoromethoxyphenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl)-
(3-Fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl )-
(3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1 -Propenyl)-
(4-Difluoromethoxyphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl)-
(4-trifluoromethylphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl)-
(3-Fluoro-4-trifluoromethylphenyl) -trans
-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl)-
(3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1 -Propenyl)-
(4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl)-
(3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-propenyl)-
(3,5-difluoro-4-chlorophenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene

6,8-Difluoro-trans-2- (trans-1-
(Butenyl)-(4-fluorophenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-
(3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-
(3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-
(3,4,5-trifluorophenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-(4
-Trifluoromethoxyphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-(3
-Fluoro-4-trifluoromethoxyphenyl) -trans
-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-
(3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1 -Butenyl)-(4
-Difluoromethoxyphenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-(4
-Trifluoromethylphenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-(3
-Fluoro-4-trifluoromethylphenyl) -trans-
1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-
(3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1 -Butenyl)-(4
-Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-(3
-Fluoro-4-chlorophenyl) -trans-1,2,3,4,4a, 9,
10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-butenyl)-
(3,5-difluoro-4-chlorophenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene

6,8-difluoro-trans-2- (trans-1-
(Pentenyl)-(4-fluorophenyl) -trans-1,2,3,4,
4a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl)-
(3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl)-
(3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl)-
(3,4,5-trifluorophenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl)-
(4-trifluoromethoxyphenyl) -trans-1,2,3,4,
4a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl)-
(3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl )-
(3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1 -Pentenyl)-
(4-Difluoromethoxyphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl)-
(4-trifluoromethylphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl)-
(3-Fluoro-4-trifluoromethylphenyl) -trans
-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl)-
(3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1 -Pentenyl)-
(4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl)-
(3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-1-pentenyl)-
(3,5-difluoro-4-chlorophenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene

6,8-difluoro-trans-2- (3-butenyl)
-(4-Fluorophenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8- Difluoro-trans-2- (3-butenyl)-(3,4,5-trifluorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro -Trans-2- (3-butenyl)-(4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a
-Octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(3-fluoro
-4-trifluoromethoxyphenyl) -trans-1,2,3,4,
4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,2,
3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(4-difluoromethoxyphenyl) -trans-1,2,3,4,4a , 9,10,10a-
Octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-
Octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(3-fluoro
-4-trifluoromethylphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(4-chlorophenyl) -trans-1,2,3,4,4a, 9,10 , 10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(3-fluoro
-4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (3-butenyl)-(3,5-difluoro- 4-chlorophenyl) -trans-1,2,3,4,4a, 9,10,10
a-octahydrophenanthrene

6,8-difluoro-trans-2- (trans-3-
(Pentenyl)-(4-fluorophenyl) -trans-1,2,3,4,
4a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl)-
(3,4-difluorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl)-
(3,5-difluorophenyl) -trans-1,2,3,4,4a, 9,10,
10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl)-
(3,4,5-trifluorophenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl)-
(4-trifluoromethoxyphenyl) -trans-1,2,3,4,
4a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl)-
(3-fluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl )-
(3,5-difluoro-4-trifluoromethoxyphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3 -Pentenyl)-
(4-Difluoromethoxyphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl)-
(4-trifluoromethylphenyl) -trans-1,2,3,4,4
a, 9,10,10a-Octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl)-
(3-Fluoro-4-trifluoromethylphenyl) -trans
-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl)-
(3,5-difluoro-4-trifluoromethylphenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3 -Pentenyl)-
(4-Chlorophenyl) -trans-1,2,3,4,4a, 9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl)-
(3-fluoro-4-chlorophenyl) -trans-1,2,3,4,4a,
9,10,10a-octahydrophenanthrene 6,8-difluoro-trans-2- (trans-3-pentenyl)-
(3,5-difluoro-4-chlorophenyl) -trans-1,2,3,
4,4a, 9,10,10a-octahydrophenanthrene

Example 11 2-Fluoro-4- (trans-7-
Preparation of propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthren-2-yl) -benzonitrile

Embedded image From Example 7, trans-7-propyl trifluoromethanesulfonate-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthren-2-yl to tetrakis (triphenylphosphine) palladium After reacting 4- (4,4-dimethyl-4,5-dihydrooxazol-2-yl) -2-fluorophenylboric acid in the presence, then reacting with phosphorus oxychloride to remove the cyano group protecting group 2-fluoro-4- (trans-7-
Propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthren-2-yl) -benzonitrile was obtained.

The following compounds are obtained in the same manner. 4- (trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10
-Octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (trans-7-ethyl-trans-4b, 5,6,7,
8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (trans-7-ethyl-trans-4b, 5,6,7,8,8a, 9,10-
Octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (trans-7-butyl-trans-4b, 5,6,7,
8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (trans-7-butyl-trans-4b, 5,6,7,8,8a, 9,10-
Octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (trans-7-pentyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile 4- (trans-7-pentyl-trans-4b, 5,6,7,8,8a, 9,10
-Octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (trans-7-hexyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile 4- (trans-7-hexyl-trans-4b, 5,6,7,8,8a, 9,10
-Octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (trans-7-heptyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile 4- (trans-7-heptyl-trans-4b, 5,6,7,8,8a, 9,10
-Octahydrophenanthrene-trans-2-yl) -benzonitrile

Example 12 2-Fluoro-4- (1-fluoro-
Preparation of trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthren-2-yl) -benzonitrile

Embedded image 8-fluoro-trans-7-propyl-trans-4b, 5,6,7,8,8a, trifluoromethanesulfonic acid obtained in Example 9
9,10-octahydrophenanthren-2-yl in the presence of tetrakis (triphenylphosphine) palladium 4- (4,4-
After reacting dimethyl-4,5-dihydrooxazol-2-yl) -2-fluorophenylboric acid, 2-fluoro-4 was obtained by reacting phosphorus oxychloride and removing the protecting group of the cyano group.
-(1-Fluoro-trans-7-propyl-trans-4b, 5,6,
7,8,8a, 9,10-Octahydrophenanthren-2-yl) -benzonitrile was obtained.

The following compounds are obtained in the same manner. 2-fluoro-4- (1-fluoro-trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene
-Trans-2-yl) -benzonitrile 4- (1-fluoro-trans-7-propyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile 2-fluoro-4- (1-fluoro-trans-7-ethyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-
Trans-2-yl) -benzonitrile 4- (1-fluoro-trans-7-ethyl-trans-4b, 5,6,7,
8,8a, 9,10-octahydrophenanthren-trans-2-yl) -benzonitrile 2-fluoro-4- (1-fluoro-trans-7-butyl-trans-4b, 5,6,7,8, 8a, 9,10-octahydrophenanthrene-
Trans-2-yl) -benzonitrile 4- (1-fluoro-trans-7-butyl-trans-4b, 5,6,7,
8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (1-fluoro-trans-7-pentyl-trans-4b, 5,6,7,8, 8a, 9,10-octahydrophenanthrene
-Trans-2-yl) -benzonitrile 4- (1-fluoro-trans-7-pentyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile 2-fluoro-4- (1-fluoro-trans-7-hexyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene
-Trans-2-yl) -benzonitrile 4- (1-fluoro-trans-7-hexyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile 2-fluoro-4- (1-fluoro-trans-7-heptyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene
-Trans-2-yl) -benzonitrile 4- (1-fluoro-trans-7-heptyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile

2-fluoro-4- (3-fluoro-trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzo Nitrile 4- (3-fluoro-trans-7-propyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile 2-fluoro-4- (3-fluoro-trans-7-ethyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-
Trans-2-yl) -benzonitrile 4- (3-fluoro-trans-7-ethyl-trans-4b, 5,6,7,
8,8a, 9,10-octahydrophenanthren-trans-2-yl) -benzonitrile 2-fluoro-4- (3-fluoro-trans-7-butyl-trans-4b, 5,6,7,8, 8a, 9,10-octahydrophenanthrene-
Trans-2-yl) -benzonitrile 4- (3-fluoro-trans-7-butyl-trans-4b, 5,6,7,
8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (3-fluoro-trans-7-pentyl-trans-4b, 5,6,7,8, 8a, 9,10-octahydrophenanthrene
-Trans-2-yl) -benzonitrile 4- (3-fluoro-trans-7-pentyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile 2-fluoro-4- (3-fluoro-trans-7-hexyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene
-Trans-2-yl) -benzonitrile 4- (3-fluoro-trans-7-hexyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile 2-fluoro-4- (3-fluoro-trans-7-heptyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene
-Trans-2-yl) -benzonitrile 4- (3-fluoro-trans-7-heptyl-trans-4b, 5,6,
7,8,8a, 9,10-octahydrophenanthrene-trans-2-
Yl) -benzonitrile

Example 13 2,6-Difluoro-4- (1-fluoro-trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10
Of (octahydrophenanthrene-trans-2-yl) -benzonitrile

Embedded image Prepared by the method of Example 7, 1-fluoro-trans-7-propyl-2- (3,5-difluorophenyl) -trans-4b, 5,6,
After lithiation of 7,8,8a, 9,10-octahydrophenanthrene with a butyllithium-hexane solution, carbon gas is reacted and 2,6-difluoro-4- (1-fluoro-trans-7-propyl- Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthren-trans-2-yl) -benzoic acid is obtained. This was converted to an acid chloride with thionyl chloride, and then reacted with ammonia to give 2,6-difluoro-4- (1-fluoro-trans-7-
Propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthren-trans-2-yl) -benzamide was obtained. By reacting this with phosphorus oxychloride and dehydrating, 2,6-difluoro-4- (1-fluoro-trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10- Octahydrophenanthrene-trans-2-yl) -benzonitrile was obtained.

The following compounds are obtained in the same manner. 2,6-difluoro-4- (trans-7-ethyl-trans-4b, 5,
6,7,8,8a, 9,10-octahydrophenanthrene-trans-
2-yl) -benzonitrile 2,6-difluoro-4- (trans-7-propyl-trans-4b,
5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (trans-7-butyl-trans-4b, 5,
6,7,8,8a, 9,10-octahydrophenanthrene-trans-
2-yl) -benzonitrile 2,6-difluoro-4- (trans-7-pentyl-trans-4b,
5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (trans-7-hexyl-trans-4b,
5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (trans-7-heptyl-trans-4b,
5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile

2,6-difluoro-4- (1,3-difluoro-trans-7-propyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2- Yl) -benzonitrile 2-fluoro-4- (1,3-difluoro-trans-7-propyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (1,3-difluoro-trans-7-propyl-trans-4b,
5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (1,3-difluoro-trans-7-ethyl
-Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (1,3-difluoro-trans-7-ethyl -Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (1,3-difluoro-trans-7-ethyl-trans-4b ,Five,
6,7,8,8a, 9,10-octahydrophenanthrene-trans-
2-yl) -benzonitrile 2,6-difluoro-4- (1,3-difluoro-trans-7-butyl
-Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (1,3-difluoro-trans-7-butyl -Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (1,3-difluoro-trans-7-butyl-trans-4b ,Five,
6,7,8,8a, 9,10-octahydrophenanthrene-trans-
2-yl) -benzonitrile 2,6-difluoro-4- (1,3-difluoro-trans-7-pentyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene- Trans-2-yl) -benzonitrile 2-fluoro-4- (1,3-difluoro-trans-7-pentyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (1,3-difluoro-trans-7-pentyl-trans-4b,
5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (1,3-difluoro-trans-7-hexyl-trans- 4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (1,3-difluoro-trans-7-hexyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (1,3-difluoro-trans-7-hexyl-trans-4b,
5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (1,3-difluoro-trans-7-heptyl-trans- 4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (1,3-difluoro-trans-7-heptyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (1,3-difluoro-trans-7-heptyl-trans-4b,
5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile

2,6-difluoro-4- (1-fluoro-trans-
7-ethyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (1-fluoro-trans- 7-butyl-trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (1-fluoro-trans- 7-pentyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (1-fluoro-trans-7-hexyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (1-fluoro-trans-7-heptyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (3-fluoro-trans-7-propyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (3-fluoro-trans-7-ethyl- Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (3-fluoro-trans-7-butyl- Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (3-fluoro-trans-7-pentyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (3-fluoro-trans-7-hexyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,6-difluoro-4- (3-fluoro-trans-7-heptyl-
Trans-4b, 5,6,7,8,8a, 9,10-octahydrophenanthrene-trans-2-yl) -benzonitrile

Example 14 trans-7-propyl-1,2,3,
Production of 4-tetrahydrophenanthren-2-ol

Embedded image (6-Methoxynaphthalen-2-yl) -acetic acid was converted to an acid chloride with thionyl chloride, and then reacted with ethylene gas at -10 ° C in the presence of aluminum chloride in methylene chloride to give 7-methoxy-3,4-dihydrochloride. -1H-phenanthrene-2-
Get on. This was reacted with a Wittig reagent prepared from methoxymethyltriphenylphosphonium chloride and potassium-t-butoxide, and the resulting enol ether was hydrolyzed with a 10% aqueous hydrochloric acid solution in THF, followed by aqueous sodium hydroxide solution in methanol. 7-methoxy-1,2,3,4-tetrahydrophenanthrene-trans-2 after isomerization
-Carbaldehyde was obtained. By reacting this with a Wittig reagent prepared from ethyltriphenylphosphonium bromide and potassium-t-butoxide,
After obtaining 7-methoxy-trans-2-propenyl-1,2,3,4-tetrahydrophenanthrene, 5% palladium / carbon (hydrous) 7-methoxy by reduction with hydrogen in the presence of a catalyst
Trans-2-propyl-1,2,3,4-tetrahydrophenanthrene is obtained. After lithiation with an n-butyllithium-hexane solution, iodine is reacted to obtain trans-7-propyl-1,2,3,4-tetrahydrophenanthren-2-ol. This compound was subjected to the same reaction as in Examples 7 to 10 to obtain the following compound.

Trans-2-propyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (3,4-difluorophenyl) -1,2,
3,4-tetrahydrophenanthrene trans-2-propyl- (3,5-difluorophenyl) -1,2,
3,4-tetrahydrophenanthrene trans-2-propyl- (3,4,5-trifluorophenyl)-
1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (3-fluoro-4-trifluoro (Methoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (3,5-difluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl -(4-difluoromethoxyphenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (4-trifluoromethylphenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (3,5 -Difluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- ( 3-fluoro-4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (3,5-difluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

Trans-2-ethyl- (4-fluorophenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3,4-difluorophenyl) -1,2,3,4
-Tetrahydrophenanthrene trans-2-ethyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3,4,5-trifluorophenyl) -1,
2,3,4-tetrahydrophenanthrene trans-2-ethyl- (4-trifluoromethoxyphenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3,5 -Difluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (4-difluoromethoxyphenyl)-
1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (4-trifluoromethylphenyl)-
1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3,5- Difluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3 -Fluoro-4-chlorophenyl) -1,
2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3,5-difluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

Trans-2-butyl- (4-fluorophenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3,4-difluorophenyl) -1,2,3,4
-Tetrahydrophenanthrene trans-2-butyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3,4,5-trifluorophenyl) -1,
2,3,4-tetrahydrophenanthrene trans-2-butyl- (4-trifluoromethoxyphenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3,5 -Difluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (4-difluoromethoxyphenyl)-
1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (4-trifluoromethylphenyl)-
1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3,5- Difluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3 -Fluoro-4-chlorophenyl) -1,
2,3,4-tetrahydrophenanthrene trans-2-butyl- (3,5-difluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

Trans-2-pentyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3,4-difluorophenyl) -1,2,
3,4-tetrahydrophenanthrene trans-2-pentyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3,4,5-trifluorophenyl) -
1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3-fluoro-4-trifluoro (Methoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3,5-difluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl -(4-difluoromethoxyphenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (4-trifluoromethylphenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3,5 -Difluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- ( 3-fluoro-4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3,5-difluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

Trans-2-hexyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3,4-difluorophenyl) -1,2,
3,4-tetrahydrophenanthrene trans-2-hexyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3,4,5-trifluorophenyl) -
1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3-fluoro-4-trifluoro (Methoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3,5-difluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl -(4-difluoromethoxyphenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (4-trifluoromethylphenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3,5 -Difluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- ( 3-fluoro-4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3,5-difluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

Trans-2-heptyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3,4-difluorophenyl) -1,2,
3,4-tetrahydrophenanthrene trans-2-heptyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3,4,5-trifluorophenyl) -
1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3-fluoro-4-trifluoro (Methoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3,5-difluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl -(4-difluoromethoxyphenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (4-trifluoromethylphenyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3,5 -Difluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- ( 3-fluoro-4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3,5-difluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

Trans-2-propyl- (4-fluorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (3,4-difluorophenylethynyl) -1,2,3,4 -Tetrahydrophenanthrene trans-2-propyl- (3,5-difluorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (4-trifluoromethoxyphenylethynyl) -1,2,3 , 4-Tetrahydrophenanthrene trans-2-propyl- (3-fluoro-4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (3,5-difluoro-4- (Trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (4-difluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (4 -Trifluoro Methylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (3-fluoro-4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl -(3,5-Difluoro-4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (4-chlorophenylethynyl) -1,
2,3,4-tetrahydrophenanthrene trans-2-propyl- (3-fluoro-4-chlorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-propyl- (3,5-difluoro-4- (Chlorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene

Trans-2-ethyl- (4-fluorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3,4-difluorophenylethynyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3,5-difluorophenylethynyl)
-Trans-1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3,4,5-trifluorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (4 -Trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3-fluoro-4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans- 2-ethyl- (3,5-difluoro-4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (4-difluoromethoxyphenylethynyl) -1,2,3 , 4-Tetrahydrophenanthrene trans-2-ethyl- (4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3-fluoro-4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrof Enanthrene trans-2-ethyl- (3,5-difluoro-4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (4-chlorophenylethynyl) -1,2,
3,4-tetrahydrophenanthrene trans-2-ethyl- (3-fluoro-4-chlorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-ethyl- (3,5-difluoro-4-chlorophenylethynyl ) -1,2,3,4-tetrahydrophenanthrene

Trans-2-butyl- (4-fluorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3,4-difluorophenylethynyl)
-1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3,5-difluorophenylethynyl)
-Trans-1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3,4,5-trifluorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (4 -Trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3-fluoro-4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans- 2-butyl- (3,5-difluoro-4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (4-difluoromethoxyphenylethynyl) -1,2,3 , 4-Tetrahydrophenanthrene trans-2-butyl- (4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3-fluoro-4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrof Enanthrene trans-2-butyl- (3,5-difluoro-4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (4-chlorophenylethynyl) -1,2,
3,4-tetrahydrophenanthrene trans-2-butyl- (3-fluoro-4-chlorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-butyl- (3,5-difluoro-4-chlorophenylethynyl ) -1,2,3,4-tetrahydrophenanthrene

Trans-2-pentyl- (4-fluorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3,4-difluorophenylethynyl) -1,2,3,4 -Tetrahydrophenanthrene trans-2-pentyl- (3,5-difluorophenylethynyl) -trans-1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3,4,5-trifluorophenylethynyl)- 1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3-fluoro-4-triethyl (Fluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3,5-difluoro-4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans- 2-pentyl- (4-difur (Romethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3 -Fluoro-4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3,5-difluoro-4-trifluoromethylphenylethynyl) -1,2,3, 4-tetrahydrophenanthrene trans-2-pentyl- (4-chlorophenylethynyl) -1,
2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3-fluoro-4-chlorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-pentyl- (3,5-difluoro-4- (Chlorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene

Trans-2-hexyl- (4-fluorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3,4-difluorophenylethynyl) -1,2,3,4 -Tetrahydrophenanthrene trans-2-hexyl- (3,5-difluorophenylethynyl) -trans-1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3,4,5-trifluorophenylethynyl)- 1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3-fluoro-4-tri (Fluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3,5-difluoro-4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans- 2-hexyl- (4-difur (Romethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3 -Fluoro-4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3,5-difluoro-4-trifluoromethylphenylethynyl) -1,2,3, 4-tetrahydrophenanthrene trans-2-hexyl- (4-chlorophenylethynyl) -1,
2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3-fluoro-4-chlorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-hexyl- (3,5-difluoro-4- (Chlorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene

Trans-2-heptyl- (4-fluorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3,4-difluorophenylethynyl) -1,2,3,4 -Tetrahydrophenanthrene trans-2-heptyl- (3,5-difluorophenylethynyl) -trans-1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3,4,5-trifluorophenylethynyl)- 1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3-fluoro-4-tri (Fluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3,5-difluoro-4-trifluoromethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans- 2-heptyl- (4-difur (Romethoxyphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3 -Fluoro-4-trifluoromethylphenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3,5-difluoro-4-trifluoromethylphenylethynyl) -1,2,3, 4-tetrahydrophenanthrene trans-2-heptyl- (4-chlorophenylethynyl) -1,
2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3-fluoro-4-chlorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene trans-2-heptyl- (3,5-difluoro-4- (Chlorophenylethynyl) -1,2,3,4-tetrahydrophenanthrene

8-fluoro-trans-2-propyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (3,4-difluorophenyl) -1 , 2,3,4-Tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (3,5-difluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (4 -Trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (3,5-difluoro-4-
(Trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans- 2-propyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (3-fluoro-4-trifluoromethylphenyl) -1,2, 3,4-tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-propyl- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

8-fluoro-trans-2-ethyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- (3,4-difluorophenyl) -1 , 2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydro Phenanthrene 8-fluoro-trans-2-ethyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- (3,5-difluoro -4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- ( 4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro- Trans-2-ethyl- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- (3,5-difluoro-4-trifluoro Methylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- (4-chlorophenyl) -1,
2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-ethyl- (3 , 5-Difluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

8-fluoro-trans-2-butyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- (3,4-difluorophenyl) -1 , 2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydro Phenanthrene 8-fluoro-trans-2-butyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- (3,5-difluoro -4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- ( 4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro- Trans-2-butyl- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- (3,5-difluoro-4-trifluoro Methylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- (4-chlorophenyl) -1,
2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-butyl- (3 , 5-Difluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

8-Fluoro-trans-2-pentyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (3,4-difluorophenyl) -1 , 2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydro Phenanthrene 8-fluoro-trans-2-pentyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (3,5-difluoro -Four-
(Trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans- 2-pentyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (3-fluoro-4-trifluoromethylphenyl) -1,2, 3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-pentyl- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

8-Fluoro-trans-2-hexyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (3,4-difluorophenyl) -1 , 2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydro Phenanthrene 8-fluoro-trans-2-hexyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (3,5-difluoro -Four-
(Trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans- 2-hexyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (3-fluoro-4-trifluoromethylphenyl) -1,2, 3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-hexyl- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

8-Fluoro-trans-2-heptyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (3,4-difluorophenyl) -1 , 2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydro Phenanthrene 8-fluoro-trans-2-heptyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (3,5-difluoro -Four-
(Trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans- 2-heptyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (3-fluoro-4-trifluoromethylphenyl) -1,2, 3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 8-fluoro-trans-2-heptyl- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

6-fluoro-trans-2-propyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (3,4-difluorophenyl) -1 , 2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (3,5-difluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (4 -Trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (3,5-difluoro-4-
(Trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans- 2-propyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (3-fluoro-4-trifluoromethylphenyl) -1,2, 3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-propyl- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

6-fluoro-trans-2-ethyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- (3,4-difluorophenyl) -1 , 2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydro Phenanthrene 6-fluoro-trans-2-ethyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- (3,5-difluoro -4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- ( 4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro- Trans-2-ethyl- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- (3,5-difluoro-4-trifluoro Methylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- (4-chlorophenyl) -1,
2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-ethyl- (3 , 5-Difluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

6-fluoro-trans-2-butyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- (3,4-difluorophenyl) -1 , 2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydro Phenanthrene 6-fluoro-trans-2-butyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- (3,5-difluoro -4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- ( 4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro- Trans-2-butyl- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- (3,5-difluoro-4-trifluoro Methylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- (4-chlorophenyl) -1,
2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-butyl- (3 , 5-Difluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

6-fluoro-trans-2-pentyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (3,4-difluorophenyl) -1 , 2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydro Phenanthrene 6-fluoro-trans-2-pentyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (3,5-difluoro -Four-
(Trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans- 2-pentyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (3-fluoro-4-trifluoromethylphenyl) -1,2, 3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-pentyl- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene

6-fluoro-trans-2-hexyl- (3,4-difluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (3,5-difluorophenyl) -Trans-1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans -2-hexyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2 , 3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (3,5-difluoro-4-
(Trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans- 2-hexyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (3-fluoro-4-trifluoromethylphenyl) -1,2, 3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-hexyl- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

6-fluoro-trans-2-heptyl- (4-fluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (3,4-difluorophenyl) -1 , 2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (3,5-difluorophenyl) -trans-1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydro Phenanthrene 6-fluoro-trans-2-heptyl- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (3,5-difluoro -Four-
(Trifluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (4-difluoromethoxyphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans- 2-heptyl- (4-trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (3-fluoro-4-trifluoromethylphenyl) -1,2, 3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (4-chlorophenyl)-
1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (3-fluoro-4-chlorophenyl) -1,2,3,4-tetrahydrophenanthrene 6-fluoro-trans-2-heptyl- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4-tetrahydrophenanthrene

4- (trans-7-propyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (trans-7-ethyl-5,6,7,8 -Tetrahydrophenanthren-2-yl) -benzonitrile 4- (trans-7-ethyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (trans-7-butyl -5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (trans-7-butyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro- 4- (trans-7-pentyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (trans-7-pentyl-5,6,7,8-tetrahydrophenanthren-2-yl ) -Benzonitrile 2-fluoro-4- (trans-7-hexyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (trans-7-hexyl-5,6,7, 8-tet (Hydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (trans-7-heptyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (trans-7-heptyl- (5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile

2-Fluoro-4- (8-fluoro-trans-7-propyl-5,6,7,8-tetrahydrophenanthren-2-yl)-
Benzonitrile 4- (8-fluoro-trans-7-propyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (8-fluoro-trans-7-ethyl- 5,6,7,8
-Tetrahydrophenanthren-2-yl) -benzonitrile 4- (8-fluoro-trans-7-ethyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (8 -Fluoro-trans-7-butyl-5,6,7,8
-Tetrahydrophenanthren-2-yl) -benzonitrile 4- (8-fluoro-trans-7-butyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (8 -Fluoro-trans-7-pentyl-5,6,
7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (8-fluoro-trans-7-pentyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4 -(8-Fluoro-trans-7-hexyl-5,6,
7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (8-fluoro-trans-7-hexyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4 -(8-Fluoro-trans-7-heptyl-5,6,
7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (8-fluoro-trans-7-heptyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile

2-Fluoro-4- (6-fluoro-trans-7-propyl-5,6,7,8-tetrahydrophenanthren-2-yl)-
Benzonitrile 4- (6-fluoro-trans-7-propyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (6-fluoro-trans-7-ethyl- 5,6,7,8
-Tetrahydrophenanthren-2-yl) -benzonitrile 4- (6-fluoro-trans-7-ethyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (6 -Fluoro-trans-7-butyl-5,6,7,8
-Tetrahydrophenanthren-2-yl) -benzonitrile 4- (6-fluoro-trans-7-butyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (6 -Fluoro-trans-7-pentyl-5,6,
7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (6-fluoro-trans-7-pentyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4 -(6-Fluoro-trans-7-hexyl-5,6,
7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (6-fluoro-trans-7-hexyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4 -(6-Fluoro-trans-7-heptyl-5,6,
7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (6-fluoro-trans-7-heptyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile

4- (6,8-Difluoro-trans-7-propyl-
5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (6,8-difluoro-trans-7-propyl-
5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2-fluoro-4- (6,8-difluoro-trans-7-ethyl-5,
6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (6,8-difluoro-trans-7-ethyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2 -Fluoro-4- (6,8-difluoro-trans-7-butyl-5,
6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (6,8-difluoro-trans-7-butyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 2 -Fluoro-4- (6,8-difluoro-trans-7-pentyl-
5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (6,8-difluoro-trans-7-pentyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzo Nitrile 2-fluoro-4- (6,8-difluoro-trans-7-hexyl-
5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (6,8-difluoro-trans-7-hexyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzo Nitrile 2-fluoro-4- (6,8-difluoro-trans-7-heptyl-
5,6,7,8-tetrahydrophenanthren-2-yl) -benzonitrile 4- (6,8-difluoro-trans-7-heptyl-5,6,7,8-tetrahydrophenanthren-2-yl) -benzo Nitrile

Example 15 trans-7-propyl-3,4,5,
Production of 6,7,8-tetrahydro-1H-phenanthren-2-one

Embedded image After reducing phenanthrene-2,7-diol with hydrogen in the presence of 5% palladium / carbon (water-containing) catalyst, it is oxidized with a mixture of chromium trioxide, sulfuric acid and water to 1,3,4,5,6,8 -Hexahydrophenanthrene-2,7-dione is obtained. After protecting one of the carbonyl groups of this compound with ethylene glycol, it is reacted with propylmagnesium bromide, dehydrated in the presence of an acid catalyst, and reapplied with a partially removed protecting group.
7-propyl-3,4,5,6-tetrahydro-1H-phenanthrene-
Obtain 2-one ethylene acetal. This is reduced with hydrogen in the presence of 5% palladium / carbon (water-containing) catalyst, and then trans-7-propyl-3,4,5,6,7 by isomerization with potassium-t-butoxide in DMF. , 8-Tetrahydro-1H-phenanthren-2-one is obtained. This compound was subjected to the same reaction as in Examples 1 to 6 to obtain the following compound.

Trans-2-propyl-trans-7- (4-fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- ( 3,4-difluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluorophenyl) -1,2, 3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- (3,4,5-trifluorophenyl) -1,2,3,4,5,6,7 , 8-Octahydrophenanthrene trans-2-propyl-trans-7- (4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl- Trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- (3,5 -Difluoro-4-
(Trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- (4-difluoromethoxyphenyl) -1,2,3,4 , 5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- (4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene Trans-2-propyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans- 7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- (4-chlorophenyl)-
1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- (3-fluoro-4-chlorophenyl) -1,2,3,4,5,6 , 7,8-Octahydrophenanthrene trans-2-propyl-trans-7- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-ethyl-trans-7- (4-fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- ( 3,4-difluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- (3,5-difluorophenyl) -1,2, 3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- (3,4,5-trifluorophenyl) -1,2,3,4,5,6,7 , 8-Octahydrophenanthrene trans-2-ethyl-trans-7- (4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl- Trans-7- (3-Fluoro-4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- (3,5 -Difluoro-4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene Trans-2-ethyl-trans-7- (4-difluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- (4- (Trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -1, 2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -1,2,3,4, 5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- (4-chlorophenyl) -1,
2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- (3-fluoro-4-chlorophenyl) -1,2,3,4,5,6,7 , 8-Octahydrophenanthrene trans-2-ethyl-trans-7- (3,5-difluoro-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-butyl-trans-7- (4-fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- ( 3,4-difluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluorophenyl) -trans-1, 2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- (3,4,5-trifluorophenyl) -1,2,3,4,5,6 , 7,8-Octahydrophenanthrene trans-2-butyl-trans-7- (4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- Butyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- (3 , 5-Difluoro-4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrofe Nthrene trans-2-butyl-trans-7- (4-difluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- (4 -Trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -1 , 2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluoro-4-trifluoromethylphenyl) -1,2,3,4 , 5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- (4-chlorophenyl) -1,
2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- (3-fluoro-4-chlorophenyl) -1,2,3,4,5,6,7 , 8-Octahydrophenanthrene trans-2-butyl-trans-7- (3,5-difluoro-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-pentyl-trans-7- (4-fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- ( 3,4-difluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluorophenyl) -trans-1, 2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- (3,4,5-trifluorophenyl) -1,2,3,4,5,6 , 7,8-Octahydrophenanthrene trans-2-pentyl-trans-7- (4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- Pentyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- (3 , 5-difluoro-4-
(Trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- (4-difluoromethoxyphenyl) -1,2,3,4 , 5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- (4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene Trans-2-pentyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans- 7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- (4-chlorophenyl)-
1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- (3-fluoro-4-chlorophenyl) -1,2,3,4,5,6 , 7,8-Octahydrophenanthrene trans-2-pentyl-trans-7- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-hexyl-trans-7- (4-fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- ( 3,4-difluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluorophenyl) -trans-1, 2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- (3,4,5-trifluorophenyl) -1,2,3,4,5,6 , 7,8-Octahydrophenanthrene trans-2-hexyl-trans-7- (4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- Hexyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- (3 , 5-difluoro-4-
(Trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- (4-difluoromethoxyphenyl) -1,2,3,4 , 5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- (4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene Trans-2-hexyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans- 7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- (4-chlorophenyl)-
1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- (3-fluoro-4-chlorophenyl) -1,2,3,4,5,6 , 7,8-Octahydrophenanthrene trans-2-hexyl-trans-7- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-heptyl-trans-7- (4-fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- ( 3,4-difluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluorophenyl) -trans-1, 2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- (3,4,5-trifluorophenyl) -1,2,3,4,5,6 , 7,8-Octahydrophenanthrene trans-2-heptyl-trans-7- (4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- Heptyl-trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- (3 , 5-difluoro-4-
(Trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- (4-difluoromethoxyphenyl) -1,2,3,4 , 5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- (4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene Trans-2-heptyl-trans-7- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans- 7- (3,5-difluoro-4-
(Trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- (4-chlorophenyl)-
1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- (3-fluoro-4-chlorophenyl) -1,2,3,4,5,6 , 7,8-Octahydrophenanthrene trans-2-heptyl-trans-7- (3,5-difluoro-4-
(Chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-propyl-trans-7- [2- (4-
Fluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- [2- (3,4-difluorophenyl) ethyl] -1 , 2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- [2- (3,5-difluorophenyl) ethyl] -1,2,3,4, 5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- [2- (3,4,5-trifluorophenyl) ethyl] -1,2,3,4,5,6, 7,8-octahydrophenanthrene trans-2-propyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene Trans-2-propyl-trans-7- [2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8
-Octahydrophenanthrene trans-2-propyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,
6,7,8-octahydrophenanthrene trans-2-propyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydro Phenanthrene trans-2-propyl-trans-7- [2- (4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl- Trans-7- [2- (3-Fluoro-4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-
Octahydrophenanthrene trans-2-propyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,
7,8-octahydrophenanthrene trans-2-propyl-trans-7- [2- (4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2 -Propyl-trans-7- [2- (3-fluoro-4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-propyl-trans-7 -[2- (3,5-difluoro-
4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-ethyl-trans-7- [2- (4-fluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl- Trans-7- [2- (3,4-difluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- [2- (3,5-difluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- [2- (3,4,5- Trifluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl]- 1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- [2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl] -1,2 , 3,4,5,6,7,8-
Octahydrophenanthrene trans-2-ethyl-trans-7- [2- (3,5-difluoro-4-
Trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,
7,8-octahydrophenanthrene trans-2-ethyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans -2-ethyl-trans-7- [2- (4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans- 7- [2- (3-Fluoro-4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- [ 2- (3,5-difluoro-4-
Trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8
-Octahydrophenanthrene trans-2-ethyl-trans-7- [2- (4-chlorophenyl)
Ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- [2- (3-fluoro-4-chlorophenyl) ethyl] -1,2 , 3,4,5,6,7,8-octahydrophenanthrene trans-2-ethyl-trans-7- [2- (3,5-difluoro-4-
Chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-butyl-trans-7- [2- (4-fluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl- Trans-7- [2- (3,4-difluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- [2- (3,5-difluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- [2- (3,4,5- Trifluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl]- 1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- [2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl] -1,2 , 3,4,5,6,7,8-
Octahydrophenanthrene trans-2-butyl-trans-7- [2- (3,5-difluoro-4-
Trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,
7,8-octahydrophenanthrene trans-2-butyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans -2-butyl-trans-7- [2- (4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans- 7- [2- (3-fluoro-4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- [ 2- (3,5-difluoro-4-
Trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8
-Octahydrophenanthrene trans-2-butyl-trans-7- [2- (4-chlorophenyl)
Ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- [2- (3-fluoro-4-chlorophenyl) ethyl] -1,2 , 3,4,5,6,7,8-octahydrophenanthrene trans-2-butyl-trans-7- [2- (3,5-difluoro-4-
Chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-pentyl-trans-7- [2- (4-
Fluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- [2- (3,4-difluorophenyl) ethyl] -1 , 2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- [2- (3,5-difluorophenyl) ethyl] -1,2,3,4, 5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- [2- (3,4,5-trifluorophenyl) ethyl] -1,2,3,4,5,6, 7,8-octahydrophenanthrene trans-2-pentyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene Trans-2-pentyl-trans-7- [2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8
-Octahydrophenanthrene trans-2-pentyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,
6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydro Phenanthrene trans-2-pentyl-trans-7- [2- (4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl- Trans-7- [2- (3-Fluoro-4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-
Octahydrophenanthrene trans-2-pentyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,
7,8-octahydrophenanthrene trans-2-pentyl-trans-7- [2- (4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2 -Pentyl-trans-7- [2- (3-fluoro-4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-pentyl-trans-7 -[2- (3,5-difluoro-
4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-hexyl-trans-7- [2- (4-
Fluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- [2- (3,4-difluorophenyl) ethyl] -1 , 2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- [2- (3,5-difluorophenyl) ethyl] -1,2,3,4, 5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- [2- (3,4,5-trifluorophenyl) ethyl] -1,2,3,4,5,6, 7,8-octahydrophenanthrene trans-2-hexyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene Trans-2-hexyl-trans-7- [2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8
-Octahydrophenanthrene trans-2-hexyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,
6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydro Phenanthrene trans-2-hexyl-trans-7- [2- (4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl- Trans-7- [2- (3-Fluoro-4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-
Octahydrophenanthrene trans-2-hexyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,
7,8-octahydrophenanthrene trans-2-hexyl-trans-7- [2- (4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2 -Hexyl-trans-7- [2- (3-fluoro-4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-hexyl-trans-7 -[2- (3,5-difluoro-
4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2-heptyl-trans-7- [2- (4-
Fluorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- [2- (3,4-difluorophenyl) ethyl] -1 , 2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- [2- (3,5-difluorophenyl) ethyl] -trans-1,2,3, 4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- [2- (3,4,5-trifluorophenyl) ethyl] -1,2,3,4,5, 6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- [2- (4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8-octa Hydrophenanthrene trans-2-heptyl-trans-7- [2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8
-Octahydrophenanthrene trans-2-heptyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethoxyphenyl) ethyl] -1,2,3,4,5,
6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7- [2- (4-difluoromethoxyphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydro Phenanthrene trans-2-heptyl-trans-7- [2- (4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl- Trans-7- [2- (3-Fluoro-4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,7,8-
Octahydrophenanthrene trans-2-heptyl-trans-7- [2- (3,5-difluoro-
4-trifluoromethylphenyl) ethyl] -1,2,3,4,5,6,
7,8-octahydrophenanthrene trans-2-heptyl-trans-7- [2- (4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2 -Heptyl-trans-7- [2- (3-fluoro-4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2-heptyl-trans-7 -[2- (3,5-difluoro-
4-chlorophenyl) ethyl] -1,2,3,4,5,6,7,8-octahydrophenanthrene

2-Fluoro-4- (trans-7-propyl-1,2,
3,4,5,6,7,8-octahydrophenanthrene-trans-2-
Yl) -benzonitrile 4- (trans-7-propyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- ( Trans-7-ethyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (trans-7-ethyl-1,2,3, 4,5,6,7,8-octahydrophenanthrene-trans-2-yl) -benzonitrile 2-fluoro-4- (trans-7-butyl-1,2,3,4,5,6,7, 8-octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (trans-7-butyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-trans-2-yl) -Benzonitrile 2-fluoro-4- (trans-7-pentyl-1,2,3,4,5,6,7,8-
Octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (trans-7-pentyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-trans-2-yl) -benzo Nitrile 2-fluoro-4- (trans-7-hexyl-1,2,3,4,5,6,7,8-
Octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (trans-7-hexyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-trans-2-yl) -benzo Nitrile 2-fluoro-4- (trans-7-heptyl-1,2,3,4,5,6,7,8-
Octahydrophenanthrene-trans-2-yl) -benzonitrile 4- (trans-7-heptyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-trans-2-yl) -benzo Nitrile

2,5-difluoro-4- (trans-7-ethyl-1,
2,3,4,5,6,7,8-octahydrophenanthrene-trans-
2-yl) -benzonitrile 2,5-difluoro-4- (trans-7-propyl-1,2,3,4,5,6,
7,8-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,5-difluoro-4- (trans-7-butyl-1,2,3,4,5,6,7,
8-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,5-difluoro-4- (trans-7-pentyl-1,2,3,4,5,6,
7,8-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,5-difluoro-4- (trans-7-hexyl-1,2,3,4,5,6,
7,8-octahydrophenanthrene-trans-2-yl) -benzonitrile 2,5-difluoro-4- (trans-7-heptyl-1,2,3,4,5,6,
7,8-octahydrophenanthrene-trans-2-yl) -benzonitrile

Trans-7-propyl-1,2,3,4,5,6,7,8-cyanophenyl 4-octanohydrophenanthrene-2-carboxylate trans-7-propyl-1,2,3,4 4,5,6,7,8-octahydrophenanthrene-2-carboxylic acid 4-cyano-3,5-difluorophenyl trans-7-ethyl-1,2,3,4,5,6,7,8-octa 4-cyanophenyl trans hydrophenanthrene-2-carboxylate-7-ethyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-2-carboxylate 4-cyano-3-fluorophenyl trans -7-ethyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-2-carboxylic acid 4-cyano-3,5-difluorophenyl trans-7-butyl-1,2,3 4,4,5,6,7,8-octahydrophenanthrene-2-carboxylate 4-cyanophenyl trans-7-butyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-2 -Carboxylic acid 4-cyano-3-fluorophenyl trans-7-butyl-1,2,3,4,5,6,7,8-octa 4-cyano-3,5-difluorophenyl trans-7-pentyl-1,2,3,4,5,6,7,8-octanohydrophenanthrene-2-carboxylate Phenyl trans-7-pentyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-2-carboxylate 4-cyano-3-fluorophenyl trans-7-pentyl-1,2,3 , 4,5,6,7,8-octahydrophenanthrene-2-carboxylic acid 4-cyano-3,5-difluorophenyl trans-7-pentyl-1,2,3,4,5,6,7,8 4-cyanophenyl trans-octahydrophenanthrene-2-carboxylate-7-pentyl-1,2,3,4,5,6,7,8-octanohydrophenanthrene-2-carboxylate 4-cyano-3-fluoro Phenyl trans-7-pentyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-2-carboxylate 4-cyano-3,5-difluorophenyl trans-7-heptyl-1,2 , 3,4,5,6,7,8-octahydrophenanthrene-2-ca 4-cyanophenyl borate trans-7-heptyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-2-carboxylate 4-cyano-3-fluorophenyl trans-7-heptyl- 1,2,3,4,5,6,7,8-octahydrophenanthrene-2-carboxylic acid 4-cyano-3,5-difluorophenyl

Trans-2- (4-Fluorophenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3,4-difluorophenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2 -(3,5-difluorophenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (4-trifluoromethoxyphenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3- Fluoro-4-trifluoromethoxyphenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3,5-difluoro-4-trifluoromethoxyphenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans -2- (4-difluoromethoxyphenyl) -trans
-7-vinyl-trans-tetrahydrophenanthrene trans-2- (4-trifluoromethylphenyl) -trans
-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3-fluoro-4-trifluoromethylphenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3,5-difluoro-4-tri (Fluoromethylphenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (4-chlorophenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene trans-2- (3-fluoro-4-chlorophenyl) -trans -
7-vinyl-trans-tetrahydrophenanthrene trans-2- (3,5-difluoro-4-chlorophenyl) -trans-7-vinyl-trans-tetrahydrophenanthrene

Trans-2- (trans-1-propenyl) -trans-7- (4-fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- ( Trans-1-propenyl) -trans-7- (3,4
-Difluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3,5
-Difluorophenyl) -trans-1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3,
4,5-trifluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (4-
(Trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3-
(Fluoro-4-trifluoromethoxyphenyl) -1,2,3,4,
5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethoxyphenyl) -1,2,3,
4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (4-
Difluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (4-
(Trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3-
(Fluoro-4-trifluoromethylphenyl) -1,2,3,4,5,
6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethylphenyl) -1,2,3,4,
5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (4-
(Chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3-
(Fluoro-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-propenyl) -trans-7- (3,5
-Difluoro-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2- (trans-1-butenyl) -trans-7- (4-fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- ( Trans-1-butenyl) -trans-7- (3,4-
Difluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3,5-
Difluorophenyl) -trans-1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3,4,5
-Trifluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (4-trifluoromethoxyphenyl)- 1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3-fluoro-4-trifluoromethoxyphenyl) -1, 2,3,4,5,
6,7,8-octahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3,5-
Difluoro-4-trifluoromethoxyphenyl) -1,2,3,
4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (4-difluoromethoxyphenyl) -1,2,3,4,5,6,7 , 8-octahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene Trans-2- (trans-1-butenyl) -trans-7- (3-fluoro-4-trifluoromethylphenyl) -1,2,3,4,5,6,
7,8-octahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3,5-
Difluoro-4-trifluoromethylphenyl) -1,2,3,4,
5,6,7,8-octahydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (4-chlorophenyl) -1,2,3,4,5,6,7,8-octa Hydrophenanthrene trans-2- (trans-1-butenyl) -trans-7- (3-fluoro-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2 -(Trans-1-butenyl) -trans-7- (3,5-
Difluoro-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2- (trans-1-pentenyl) -trans-7- (4-fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- ( Trans-1-pentenyl) -trans-7- (3,4
-Difluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3,5
-Difluorophenyl) -trans-1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3,
4,5-trifluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (4-
(Trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3-
(Fluoro-4-trifluoromethoxyphenyl) -1,2,3,4,
5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethoxyphenyl) -1,2,3,
4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (4-
Difluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (4-
(Trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3-
(Fluoro-4-trifluoromethylphenyl) -1,2,3,4,5,
6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethylphenyl) -1,2,3,4,
5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (4-
(Chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3-
(Fluoro-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-1-pentenyl) -trans-7- (3,5
-Difluoro-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (4-
(Fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,4
-Difluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,5
-Difluorophenyl) -trans-1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,
4,5-trifluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (4-
(Trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3-
(Fluoro-4-trifluoromethoxyphenyl) -1,2,3,4,
5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethoxyphenyl) -1,2,3,
4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (4-
Difluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (4-
(Trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3-
(Fluoro-4-trifluoromethylphenyl) -1,2,3,4,5,
6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,5
-Difluoro-4-trifluoromethylphenyl) -1,2,3,4,
5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (4-
(Chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3-
Fluoro-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (trans-3-pentenyl) -trans-7- (3,5
-Difluoro-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene

Trans-2- (3-butenyl) -trans-7- (4-
(Fluorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3,4-difluorophenyl) -1,2, 3,4,5,6,7,8-octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3,5-difluorophenyl) -trans-1,2,3,4,5, 6,7,8-octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3,4,5-trifluorophenyl) -1,2,3,4,5,6,7,8 -Octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3-fluoro-4-
(Trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3,5-difluoro
-4-trifluoromethoxyphenyl) -1,2,3,4,5,6,7,8-
Octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (4-difluoromethoxyphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (3 -Butenyl) -trans-7- (4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3-fluoro-4-
(Trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3,5-difluoro
-4-trifluoromethylphenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (4-chlorophenyl) -1, 2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3-fluoro-4-
(Chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene trans-2- (3-butenyl) -trans-7- (3,5-difluoro
-4-chlorophenyl) -1,2,3,4,5,6,7,8-octahydrophenanthrene

Example 16 Preparation of Liquid Crystal Composition 1 Host liquid crystal composition (H-1) having the following composition

Embedded image Was prepared. Here, the physical property values of (H-1) are as follows. Nematic phase upper limit temperature (T _NI ): 116.7 ° C. Solid phase or smectic phase-nematic phase transition temperature (T → _N ): 11 ° C. Threshold voltage (Vth): 2.14 V Dielectric anisotropy (Δε): 4.8 Different refractive index Anisotropy (Δn): 0.090 The measurement was performed at 20 ° C.

The parent liquid crystal (H) obtained in Example 1 was 80%.
(Iac-1)

Embedded image When a liquid crystal composition (M-1) consisting of 20% was prepared, (M-
Physical properties of 1) were as follows. Nematic phase upper limit temperature (T _NI ): 107.9 ° C. Solid phase or smectic phase-nematic phase transition temperature (T → _N ): -13 ° C. Threshold voltage (Vth): 1.92 V Dielectric anisotropy (Δε): 4.5 Refractive index Anisotropy (Δn): 0.085 From this result, it can be seen that equation (Iac-1) can effectively reduce T → _N without reducing the threshold voltage and deteriorating other characteristics.

(Comparative Example 1) Compound (R-1) having a similar structure in place of (Iac-1)

Embedded image The compound (H) was added to (H) in the same amount (20% by weight) to obtain a liquid crystal composition (MR-1) having the following physical properties. Nematic phase upper limit temperature (T _NI ): 109.4 ° C. Solid phase or smectic phase-nematic phase transition temperature (T → _N ): 15 ° C. Threshold voltage (Vth): 1.79 V Dielectric anisotropy (Δε): 7.0 Different refractive index It can be seen that the anisotropy (Δn): 0.087 (R-1) has an extremely high effect of reducing the threshold voltage when added to (H-1), but is inferior to the effect of reducing T → _N.

Example 17 Preparation of Liquid Crystal Composition 2 Host liquid crystal composition (H-2) having the following composition:

Embedded image Was prepared. Here, the physical property values of (H-2) are as follows. Nematic phase upper limit temperature (T _NI ): 54.5 ° C Solid phase or smectic phase-nematic phase transition temperature (T → _N ): -40 ° C. Threshold voltage (Vth): 1.60 V Dielectric anisotropy (Δε): 6.7 Performed at 20 ° C.

The base liquid crystal (H-2) was 80% and obtained in Example 1 (Iah-1).

Embedded image When a liquid crystal composition (M-2) consisting of 20% was prepared, (M-
Physical properties of 2) were as follows. Nematic phase upper limit temperature (T _NI ): 64.5 ° C Solid phase or smectic phase-nematic phase transition temperature (T → _N ): -60 ° C Threshold voltage (Vth): 1.49V Dielectric anisotropy (Δε): 8.2 Result This shows that equation (Iah-1) also has a T → _N reduction effect.

(Comparative Example 2) Compound (R-2) having a similar structure in place of (Iac-1)

Embedded image The physical properties of the liquid crystal composition (MR-2) obtained by adding the same compound (H-2) to (H-2) in the same amount (20% by weight) were as follows. Nematic phase upper limit temperature (T _NI ): 67.2 ° C. Solid phase or smectic phase-nematic phase transition temperature (T → _N ): -40 ° C. Threshold voltage (Vth): 1.44 V Dielectric anisotropy (Δε): 9.1 (R It can be seen that the addition of (-2) to (H-2) has an extremely high effect of reducing the threshold voltage, but has almost no effect of reducing T → _N.

Example 18 Preparation of Liquid Crystal Composition 3 Host liquid crystal composition (H-3) having the following composition:

Embedded image Was prepared. Here, the physical property values of (H-3) are as follows. Nematic phase upper limit temperature (T _NI ): 75.0 ° C. Solid phase or smectic phase-nematic phase transition temperature (T → _N ): -70 ° C. Threshold voltage (Vth): 1.49 V Dielectric anisotropy (Δε): 10.3 Dielectric constant Anisotropy (Δε): 0.142

The parent liquid crystal (H-3) was 90% and obtained in Example 1 (Iac-1).

Embedded image A liquid crystal composition (M-3) consisting of 10% was prepared. This composition also shows good low-temperature stability, and (Iac-1) has excellent compatibility with a wide range of liquid crystal materials.

[0222]

Industrial Applicability The compound represented by the general formula (I) according to the present invention can be produced very easily industrially as shown in Examples, and chemically reacts with heat, light, water and the like. Stable and
It has excellent compatibility with the parent liquid crystal which is currently widely used as a nematic liquid crystal. Moreover, by adding a small amount to the base liquid crystal, the solid phase or the smectic phase-nematic phase transition temperature can be reduced, and the precipitation can be suppressed. Therefore, it is suitable for various liquid crystal display elements requiring a wide operating temperature range, and is very useful as a liquid crystal material.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09K 19/34 C09K 19/34 G02F 1/13 500 G02F 1/13 500 (72) Inventor Haruyoshi Takatsu Higashiyamato-shi, Tokyo 3-6-27 Nakahara (72) Inventor Gerwald Grahe Berlin, Germany Reichhal Tostrasse 13 14195 (72) Inventor Rainer Bruno Frings, Germany Berlin Pet Petser Strasse 16A 12307 (72) Inventor Cornelia Pitthard, Germany Berlin Hirschhorner Bake 28 14 163

Claims (14)

[Claims] 1. A compound of the general formula (I)(Wherein R is an alkyl group having 1 to 16 carbon atoms or an alcohol)
Xyl group, alkenyl group having 2 to 16 carbon atoms, 3 carbon atoms
~ 16 alkenyloxy groups, or 1-10 carbon atoms
Alkyl having 1 to 12 carbon atoms substituted with an alkoxy group
Represents a group, which may be substituted with halogen,
Ring A and ring C are each independently one C
H_TwoTwo or more CHs that are not groups or adjacent_TwoIf the group is -O-
Or trans-1,4-cyclo which may be replaced by -S-
Xylene group, one CH group present in the group or adjacent
Not two or more CH groups may be replaced by -N =
Phenylene group, 1,4-cyclohexenylene group, 1,4-bisic
B (2.2.2) octylene group, piperidine-1,4-diyl group, na
Phthalene-2,6-diyl group, trans-decahydronaphthale
1-trans-2,6-diyl group or 1,2,3,4-tetrahydro
Ronaphthalene-2,6-diyl group, these are cyano group
Or ring B may be substituted with halogen.(Wherein the cyclohexane ring represents trans,
And it may be substituted with a halogen group or halogen. )
Represents the difference, L¹, L^TwoAnd L^ThreeAre independently -CH_Two-C
H_Two-, -C≡C-,-(CH_Two)_Four-, -CF = CF-, -OCH_Two-, -CH_TwoO-, -O
CF_Two-, -CF_TwoO-, -CO _Two-, -OCO-, -CH = N-N = CH-, -CH = CH-CH
_Two-CH_Two-, -CH_Two-CH_Two-CH = CH- or a single bond, m and
n independently represents 0 or 1, but m + n ≦ 1
X¹And X^TwoAre independently hydrogen and chlorine atoms
Y represents a hydrogen atom, a fluorine atom,
Chlorine atom, trifluoromethoxy group, difluoromethoxy
Si group, trifluoromethyl group, 2,2,2-trifluoroeth
Xy group, cyano group, linear alkyl having 1 to 12 carbon atoms
Group, a straight-chain alkenyl group having 2 to 12 carbon atoms and a straight-chain alkenyl group having 1 to 12 carbon atoms.
Chain alkyloxy group or 2 to 12 linear alkene
Represents a loxy group, and the constituent elements of this compound are
Where there is an asymmetric carbon
May be optically active or racemic,
Ring B represents tetradecahydrophenanthrene, Y is not substituted
Substituted alkyl, unsubstituted alkoxy or cyano
Represents a group, L^ThreeBut -CO_TwoX for-or -OCO-¹And X^Two
Either represents a chlorine atom or a fluorine atom, and ring A
Or a cyano group other than the 2- and 7-positions of ring C or ring B
L¹, L^TwoAnd L^ThreeAre independently -CH_Two-CH_Two-,-
(CH_Two)_Four-, -CF = CF-, -OCH_Two-, -CH_TwoO-, -OCF_Two-, -CF_TwoO-,
-CO_Two-, -OCO-, -CH = N-N = CH-, -CH = CH-CH_Two-CH_Two-, -CH_Two-C
H_Two-CH = CH- or a single bond. )
Enanthrene derivatives. 2. The ring A and the ring C each independently represent a 1,4-phenylene group or a trans-1,4-cyclohexylene group which may be substituted by a fluorine atom. A compound as described. 3. L ¹ , L ² and L ³ are each independently -CH ₂ -C
_2. The compound according to claim 1, which represents H ₂ -or a single bond. 4. The compound according to claim 1, wherein m and n represent 0. 5. In the general formula (I), ring B is 2. The compound according to claim 1, wherein the stereochemistry of the cyclohexane ring represents trans, and the hydrogen atom on the aromatic ring may be substituted with a cyano group or a halogen. 6. In the general formula (I), ring B is Wherein the stereochemistry of the cyclohexane ring represents trans, and the hydrogen atom on the aromatic ring may be substituted by a fluorine atom, and m and n represent 0. The compound according to 1. 7. The compound according to claim 6, wherein L ³ in formula (I) represents a single bond. 8. In the general formula (I), R represents 1 to 1 carbon atoms.
Represents a linear alkyl group of 2 or a linear alkenyl group of 2 to 12 carbon atoms, Y is a fluorine atom, a chlorine atom, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, 3,3,3 8. The compound according to claim 1, which represents a trifluoroethoxy group or a cyano group. 9. In the general formula (I), R represents 1 to 7 carbon atoms.
Represents a linear alkyl group or a linear alkenyl group having 2 to 7 carbon atoms, and X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom.
A compound as described. 10. The compound according to claim 1, wherein in the general formula (I), Y represents a fluorine atom or a cyano group. 11. A liquid crystal composition comprising at least one hydrophenanthrene derivative represented by the general formula (I) according to claim 1. 12. A liquid crystal display device using the liquid crystal composition according to claim 11. 13. An active matrix driven liquid crystal display device using the liquid crystal composition according to claim 11. 14. A super-twisted nematic liquid crystal display device using the liquid crystal composition according to claim 11.